CN102977615B - Modified rosin tackifying resin as well as preparation method and application thereof - Google Patents
Modified rosin tackifying resin as well as preparation method and application thereof Download PDFInfo
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- CN102977615B CN102977615B CN201210567579.0A CN201210567579A CN102977615B CN 102977615 B CN102977615 B CN 102977615B CN 201210567579 A CN201210567579 A CN 201210567579A CN 102977615 B CN102977615 B CN 102977615B
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- 229920005989 resin Polymers 0.000 title claims abstract description 110
- 239000011347 resin Substances 0.000 title claims abstract description 110
- 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 105
- 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 105
- 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 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 monoterpene compounds Chemical class 0.000 claims abstract description 56
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 40
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229930003658 monoterpene Natural products 0.000 claims abstract description 9
- 235000002577 monoterpenes Nutrition 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 24
- 235000019260 propionic acid Nutrition 0.000 claims description 20
- 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 claims description 20
- 238000009835 boiling Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 10
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 4
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 claims description 3
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 claims description 3
- 235000001510 limonene Nutrition 0.000 claims description 3
- 229940087305 limonene Drugs 0.000 claims description 3
- 150000007875 phellandrene derivatives Chemical class 0.000 claims description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 2
- IHPKGUQCSIINRJ-CSKARUKUSA-N (E)-beta-ocimene Chemical compound CC(C)=CC\C=C(/C)C=C IHPKGUQCSIINRJ-CSKARUKUSA-N 0.000 claims description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- MUQDLKRGXFYZKI-UHFFFAOYSA-N CC(C)(C)C(C=C1C(C)(C)C)=CC(CCCC(C(O)=O)SC(CCCC(C=C(C(C)(C)C)C=C2C(C)(C)C)=C2O)C(O)=O)=C1O Chemical compound CC(C)(C)C(C=C1C(C)(C)C)=CC(CCCC(C(O)=O)SC(CCCC(C=C(C(C)(C)C)C=C2C(C)(C)C)=C2O)C(O)=O)=C1O MUQDLKRGXFYZKI-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 2
- 229930006722 beta-pinene Natural products 0.000 claims description 2
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 150000002989 phenols Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000004831 Hot glue Substances 0.000 description 18
- 238000010792 warming Methods 0.000 description 12
- 238000007701 flash-distillation Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VLTOSDJJTWPWLS-UHFFFAOYSA-N pent-2-ynal Chemical compound CCC#CC=O VLTOSDJJTWPWLS-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to modified rosin resin and discloses modified rosin tackifying resin as well as a preparation method and application thereof. The preparation method comprises the following steps of: uniformly mixing rosin or rosin derivatives, monoterpene compounds, dicyclopentadiene fractions and catalysts in an autoclave; replacing air in the autoclave by use of nitrogen or carbon dioxide; reacting the mixture at a pressure of 0.2-0.6 Mpa and at 170-290 DEG C for 1 hour to 30 hours; and decompressing after the reaction, and removing low-boiling-point substances, thus obtaining the modified rosin tackifying resin, or adding an antioxidant stabilizer into the mixture at 200-230 DEG C, thus obtaining the modified rosin tackifying resin with higher quality. The softening point of the modified rosin tackifying resin ranges from 80 DEG C to 110 DEG C, the acid value of the tackifying resin is 15-70mg KOH per gram, and the color of the tackifying resin is less than No.6 Ghana color. The modified rosin tackifying resin can be widely applied to the field of tackifiers, coating paint, printing ink and the like, and especially can be applied to the field of metallocene catalysis polyolefin tackifiers.
Description
Technical field
The present invention relates to modified rosin resin, particularly a kind of modified rosin tackifying resin and preparation method thereof and application.
Background technology
China's pine tree aboundresources, its rosin produced is the most important product of China's chemistry of forest product industry, is also mainstay industry.Gum Rosin is the resin obtained by rosin or modified rosin and alcohol or other material modified reaction, and modified rosin resin has been widely used in hot melt adhesive, pressure sensitive adhesive, footwear glue, multiple film glue, seal gum; Rosin ester can also make the properties-correcting agent of rubber and plastics.
The main component of hot melt adhesive is main polymer, tackifying resin, viscosity modifier and filler etc., the difference of its classification Main Basis main polymer.Maximum hot melt adhesives is EVA(ethylene-vinyl acetate copolymer) class and styrene block elastomerics class, the former is mainly used in the hot melt adhesive products such as packaging, adhesive bookbinding, carpenter's furniture, and the latter is mainly used in disposable sanitary product and non-setting adhesive goods.Polyolefine comprises polyethylene, atactic polyolefin (APAO) and metallocene (Metallocene) polymkeric substance etc., and this hot melt adhesive is used for the industries such as footwear industry, packaging.
EVA hot-melt adhesive is since the sixties in 20th century comes out, become one of tackiness agent that China is most widely used, consumption is maximum, but that its main drawback is bonding strength is lower, not high-low temperature resistant and not resistance to fatty wet goods, and these chemical structure characteristics by EVA determine.Therefore, in the production and use procedure of EVA hot-melt adhesive, often there is the disadvantages such as irritating smell is large, charing skinning, bad thermo-oxidative stability, poor high/low temperature adhesiveproperties, polymkeric substance (polyethylene etc. as the traditional) difficulty that other degree of crystallinity are higher is used in hot melt adhesive.The appearance of metallocene catalyzed polyolefin, changes the above-mentioned view of industry to hot melt adhesive.Polyolefin elastomer product line, under various different temperature condition, all has the saving on good bond properties and significant glue consumption, and polyolefin elastomer has unique chemical attribute, and the characteristic such as high workability, low-crystallinity and lower molecular weight.The performance advantage that metallocene catalyzed polyolefin provides, for hot fusible adhesive for package brings the solution of innovation, also provides unprecedented possibility in other more hot melt adhesive Application Areass.This type of material can be the advantage that hot-melt adhesive brings in many processing characteristicies of the saving comprised on better bounding force, glue consumption, wider Applicable temperature scope and Non-carbonized tasteless than EVA class.
The current tackifying resin that can be used for polyolefins tackiness agent mainly contains C5 petroleum resin, terpine resin, hydrogenation C5 petroleum resin and staybelite, wherein C5 petroleum resin, terpine resin, hydrogenation C5 petroleum resin must be taked with aluminum chloride, boron trifluoride is the positively charged ion cold polymerization explained hereafter of catalyzer, this technique need strong condensing equipment and reaction the later stage need by material and washing, and then distillation is except desolventizing, this produced in series flow process produces a large amount of waste water and consumes the very high energy, and C5 petroleum fractions is as Nonrenewable resources, it has one day that consumes exhaustion eventually.And staybelite is due to the low shortcoming of its softening temperature, limit its application in hot melt adhesive field.Therefore develop a kind of sustainable tackifying resin to meet day by day widely used polyolefins tackiness agent and become and become current problem urgently to be resolved hurrily.
For dicyclic pentylene modified Gum Rosin, a kind of preparation method is proposed: dicyclopentadiene: the molal quantity ratio of rosin=1:0.5 ~ 2 in patent ZL 200610012862.1, at 240 ~ 260 DEG C, under 0.5 ~ 1.3Mpa pressure, react 6 ~ 10 hours, then reduce pressure, distill out low cut and obtain dicyclic pentylene modified Gum Rosin product.Obtained product colour is 6 ~ 9(Jia Shi colorimetric number), resin softening point 110 ~ 140 DEG C.Adopt above method to produce dicyclic pentylene modified Gum Rosin, mainly contain following shortcoming: one is that when producing, pressure is large, high to equipment requirements; Two is that product colour is dark, ink etc. can only be applied to low place is required to color, at adhesive area, resin itself must have good consistency with tackiness agent bulk elastomer material, and the shortcoming of resin and polyolefins poor compatibility limits its application in this field; Three is that resin softening point is higher, and the application in tackiness agent is also restricted.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, provides a kind of preparation method of modified rosin tackifying resin.
Another object of the present invention is to provide a kind of modified rosin tackifying resin prepared by above-mentioned preparation method.
Another object of the present invention is the application providing above-mentioned modified rosin tackifying resin.
Object of the present invention is achieved through the following technical solutions:
A preparation method for modified rosin tackifying resin, comprises the steps:
Toward in autoclave, add rosin or rosin derivative, monoterpenes compound, dicyclopentadiene cut and catalyzer, mix, go out air with nitrogen or carbon dioxide replacement, then react 1 ~ 30 hour at pressure 0.2 ~ 0.6Mpa, temperature 170 ~ 290 DEG C, reaction terminates rear decompress(ion), and namely removing low-boiling point material obtains modified rosin tackifying resin.
For obtaining higher-quality modified rosin tackifying resin, adding antioxidant stabilizer again in 200 ~ 230 DEG C after above-mentioned preparation method is also included in and obtains modified rosin tackifying resin and stirring, making its effect better.
Described rosin is preferably gum resin or toll oil rosin etc.; Described rosin derivative is preferably staybelite, nilox resin or resin etc.
Described monoterpenes compound be preferably in turps, phellandrene, kautschin, limonene, α-pinene, beta-pinene, myrcene and ocimene one or more.Adding monoterpenes compound can make resin and metallocene catalyzed polyolefin consistency significantly improve.
The content of the dicyclopentadiene in described dicyclopentadiene cut is preferably 50 ~ 100wt%, and the content of the dicyclopentadiene in preferred described dicyclopentadiene cut is 75 ~ 98wt%.Dicyclopentadiene cut obtains from petroleum cracking Crude products.deep process, coal oil refining byproduct or other approach.
Described catalyzer is preferably phenols sulfide; Preferred, described catalyzer is the phenols sulfide with following structure:
Wherein, x=0,1,2 or 3; Y is the integer between 0 ~ 100; R is hydrocarbon group; As Antioxidant300-4, the ROSINOX of 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), French Arkema
tM, VULTAC 2, the ETHANOX 323 of Albemarle Corporation of the U.S., the GY-323 of Guangzhou synthetic materials institute.Catalyzer can eliminate partly conjugated double bond, to preventing the oxidation of modified rosin resin from playing good effect, plays bleaching action at high temperature to modified rosin resin simultaneously.
The add-on of described dicyclopentadiene cut and the mass ratio of rosin or rosin derivative are preferably 0.44 ~ 1.22; The add-on of described monoterpenes compound is preferably filled a prescription total mass (rosin or rosin derivative, monoterpenes compound, the quality of dicyclopentadiene cut and catalyzer and) 5 ~ 15%, the add-on of described catalyzer is preferably 0.1 ~ 0.5% of rosin or rosin derivative amount.
The method of described removing low-boiling point material is preferably flash evaporation.
Described antioxidant stabilizer is preferably 2, 6-di-tert-butyl-4-methy phenol, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), β-(4-hydroxy phenyl-3, 5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, 2 '-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate] at least one and tricresyl phosphite (nonyl phenyl ester), three (2, 4-di-tert-butyl-phenyl) mixture of at least one in phosphorous acid ester and triphenyl phosphite, but be not limited to above-mentioned compound, preferred, described antioxidant stabilizer is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) mixture of phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid is preferably 0.6 ~ 3:1.
The add-on of described antioxidant stabilizer is preferably 0.2 ~ 0.5% of rosin or rosin derivative amount.
A kind of modified rosin tackifying resin is prepared by above-mentioned preparation method.The softening temperature of described modified rosin tackifying resin is 80 ~ 110 DEG C, and acid number is 15 ~ 70mgKOH/g, and color is less than Ghana's look number No. 6 looks.
Above-mentioned modified rosin tackifying resin can be widely used in the fields such as tackiness agent, paint of coating and ink, the application particularly in metallocene catalyzed polyolefin adhesive area.
The present invention has following advantage and effect relative to prior art:
(1) method that the present invention prepares modified rosin tackifying resin is prepared under lower pressure condition, not high to equipment requirements.
(2) the modified rosin tackifying resin softening temperature that prepared by the present invention is 80 ~ 110 DEG C, acid number is 15 ~ 70mgKOH/g, color is less than Ghana's look number No. 6 looks, and the dicyclo modified rosin resin softening temperature of conventional invention is 110 ~ 140 DEG C, and acid number is 5 ~ 30mgKOH/g, color Ghana look number 6 ~ No. 9 looks, because resin softening point of the present invention is lower, consistency is better, and color is better, therefore Application Areas is extensive, can be applied to the fields such as tackiness agent, paint of coating and ink.
(3) the modified rosin tackifying resin prepared of the present invention is compared with traditional ester gum, pentalyn, dcpd resin and Abietyl modified dcpd resin, resin of the present invention and metallocene catalyzed polyolefin consistency good, change the present situation that present stage Gum Rosin, dcpd resin and Abietyl modified dcpd resin can not be applied to metallocene catalyzed polyolefin.
(4) the modified rosin tackifying resin prepared of the present invention, because rosin contains carboxyl polar group, make have better wettability and sticking power with non-polar materials such as the hot melt adhesive of the hot melt adhesive ratio terpine resin of this resin formulations, the preparation of C5 petroleum resin and PP, PET under equivalent formulation.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The rosin that following examples are selected is superfine rosin, acid number 169(mgKOH/g), softening temperature 77 DEG C, being dissolved in Ghana's look that toluene is made into 50wt% solution is 5+.
Cloud point (1:1Affinity GA1950) refers to that modified rosin tackifying resin mixes at 180 DEG C with the ratio of 1:1 with Afnity GA1950, then with the cooling rate cooling of per minute decline 5 degree, when sample is cooled to the temperature occurring the most micro-waxy crystalline the earliest.
Embodiment 1
Be add 365 grams of rosin in the autoclave of 1L toward volume, 0.37 gram 300, the dicyclopentadiene cut of 275 grams of dicyclopentadiene content 83wt%, 33.73 grams, turps, 265 DEG C are warming up in 2 hours, pressure is 0.52Mpa, react 2 hours, decompress(ion), flash distillation removing low-boiling point material, then 220 DEG C are cooled to, add 0.36 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.36 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, obtain modified rosin tackifying resin.The softening temperature of this resin is 93 DEG C, acid number: 34.2(mgKOH/g), color: Ghana's look 3.5, cloud point (1:1Affinity GA1950) <25 DEG C.
Embodiment 2
Be add 365 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 275 grams of dicyclopentadiene content 83wt%, 45 grams, turps, be warming up to 265 DEG C in 2 hours, pressure is 0.52Mpa, reacts 5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 220 DEG C, adds 0.73 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1.1 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 94 DEG C, acid number: 35.3(mgKOH/g), color: Ghana's look 4, cloud point (1:1Affinity GA1950) <25 DEG C.
Embodiment 3
Be add 300 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 335 grams of dicyclopentadiene content 83wt%, 45 grams, turps, be warming up to 265 DEG C in 2 hours, pressure is 0.55Mpa, reacts 3.5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 220 DEG C, adds 0.6 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 105 DEG C, acid number: 21.3(mgKOH/g), color: Ghana look 4+, cloud point (1:1AffinityGA1950) 32 DEG C.
Embodiment 4
Be add 275 grams of rosin in the autoclave of 1L toward volume, 0.9 gram of ETHANOX 323, the dicyclopentadiene cut of 335 grams of dicyclopentadiene content 83wt%, 45 grams, turps, 265 DEG C are warming up in 2 hours, pressure is 0.60Mpa, react 4 hours, decompress(ion), flash distillation removing low-boiling point material, then 230 DEG C are cooled to, add 0.45 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, obtain modified rosin tackifying resin.The softening temperature of this resin is 115 DEG C, acid number: 19.5(mgKOH/g), color: Ghana look 3+, cloud point (1:1AffinityGA1950) 43 DEG C.
Embodiment 5
Be add 420 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 185 grams of dicyclopentadiene content 75wt%, 45 grams, turps, be warming up to 265 DEG C in 2 hours, pressure is 0.43Mpa, reacts 5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 210 DEG C, adds 0.9 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 85.5 DEG C, acid number: 65.5(mgKOH/g), color: Ghana's look 3, cloud point (1:1Affinity GA1950) <25 DEG C.
Embodiment 6
Be add 420 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 185 grams of dicyclopentadiene content 50wt%, limonene 45 grams, be warming up to 265 DEG C in 2 hours, pressure is 0.45Mpa, reacts 5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 200 DEG C, adds 0.45 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.45 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 80.5 DEG C, acid number: 69.5(mgKOH/g), color: Ghana's look 3.Cloud point (1:1Affinity GA1950) <25 DEG C.
Embodiment 7
Be add 300 grams of rosin in the autoclave of 1L, 0.6 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 335 grams of dicyclopentadiene content 83wt%, phellandrene 45 grams, be warming up to 265 DEG C in 2 hours, pressure is 0.56Mpa, reacts 5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 220 DEG C, adds 0.45 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 105 DEG C, acid number: 22.5(mgKOH/g), color: Ghana's look 4, cloud point (1:1Affinity GA1950) 33 DEG C.
Embodiment 8
Be add 300 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 305 grams of dicyclopentadiene content 93wt%, 45 grams, turps, be warming up to 265 DEG C in 2 hours, pressure is 0.32Mpa, reacts 5 hours, decompress(ion), flash distillation removing low-boiling point material, then cools to 220 DEG C, adds 0.45 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.6 gram three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stirs releasing in 10 minutes, obtains modified rosin tackifying resin.The softening temperature of this resin is 101 DEG C, acid number: 23.5(mgKOH/g), color: Ghana's look 4, cloud point (1:1AffinityGA1950) 28 DEG C.
Embodiment 9
Be add 375 grams of rosin in the autoclave of 1L toward volume, 0.9 gram of VULTAC 2, the dicyclopentadiene cut of 225 grams of dicyclopentadiene content 98wt%, 65 grams, turps, 265 DEG C are warming up in 2 hours, pressure is 0.2Mpa, react 4.5 hours, decompress(ion), flash distillation removing low-boiling point material, then 220 DEG C are cooled to, add 0.7 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.75 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, obtain modified rosin tackifying resin.The softening temperature of this resin is 95 DEG C, acid number: 29.5(mgKOH/g), color: Ghana look 4-, cloud point (1:1AffinityGA1950) 35 DEG C.
Embodiment 10
Be add 335 grams of rosin in the autoclave of 1L toward volume, 1.68 gram GY-323, the dicyclopentadiene cut of 275 grams of dicyclopentadiene content 100wt%, 107.94 grams, turps, 265 DEG C are warming up in 2 hours, pressure is 0.60Mpa, react 5 hours, decompress(ion), flash distillation removing low-boiling point material, then 220 DEG C are cooled to, add 0.45 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, obtain modified rosin tackifying resin.The softening temperature of this resin is 108 DEG C, acid number: 25.5(mgKOH/g), color: Ghana look 3+, cloud point (1:1Affinity GA1950 DEG C.
Comparative example 1(comparative example 3)
Be add 300 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tMthe dicyclopentadiene cut of 335 grams of dicyclopentadiene content 83wt%, 265 DEG C are warming up in 2 hours, pressure is 0.55MPa, react 5 hours, decompress(ion), Temperature fall, to 220 DEG C, removes low-boiling point material, add 0.6 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.3 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, the softening temperature obtaining resin is 108 DEG C, acid number: 24(mgKOH/g), color: Ghana's look 4, cloud point (1:1Affinity GA1950) 105 DEG C.
Comparative example 2(comparative example 2)
Be add 365 grams of rosin in the autoclave of 1L, 0.9 gram of ROSINOX toward volume
tM, the dicyclopentadiene cut of 275 grams of dicyclopentadiene content 83wt%, is warming up to 265 DEG C in 2 hours, pressure is 0.52Mpa, react 5 hours, decompress(ion), flash distillation removing low-boiling point material, then 220 DEG C are cooled to, add 0.73 gram of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1.1 gram of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, stir releasing in 10 minutes, obtain modified rosin tackifying resin.The softening temperature of this resin is 94 DEG C, acid number: 36.2(mgKOH/g), color: Ghana's look 4, cloud point (1:1Affinity GA1950) 85 DEG C.
By modified rosin tackifying resin of the present invention and similar products at home and abroad, the consistency in metallocene catalyzed polyolefin AffinityGA1950 (cloud point) test and comparison, the results are shown in Table 1.
Table 1
As can be seen from Table 1, the consistency of modified rosin tackifying resin of the present invention and metallocene catalyzed polyolefin Affinity 1950 can compare favourably with terpine resin, C5 petroleum resin completely.
The Comparison study of resin in metallocene catalyzed polyolefin hot melt adhesive:
By the similar products at home and abroad that the index such as softening temperature, color and modified rosin tackifying resin of the present invention (embodiment 8) are close, with resin 48wt%, Affinity GA1950 elastomerics 35wt%, paraffin 15wt%, adhesion promoter pp-1101wt%, the same recipe of antioxidant 1010 1wt% is mixed with hot melt adhesive at 175 DEG C, and test hot melt adhesive is to the adhesiveproperties of PET, and result is as table 2.
Table 2
As can be seen from Table 2, technical indicator and other like products of modified rosin tackifying resin of the present invention are close, introduce material-rosin due to modified rosin tackifying resin and still remain with part carboxyl after the reaction, improve the wetting ability of material to low-surface-energy material, make the adhesive effect of metallocene catalyzed polyolefin hot melt adhesive to the difficult sticky material such as PE, PET made of resin of the present invention be better than common terpine resin, C5 petroleum resin, therefore modified rosin tackifying resin of the present invention can be widely used in adhesive area.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a modified rosin tackifying resin, it is characterized in that comprising the steps: toward in autoclave, add rosin or rosin derivative, monoterpenes compound, dicyclopentadiene cut and catalyzer, mix, air is gone out with nitrogen or carbon dioxide replacement, then react 1 ~ 30 hour at pressure 0.2 ~ 0.6Mpa, temperature 170 ~ 290 DEG C, reaction terminates rear decompress(ion), and namely removing low-boiling point material obtains modified rosin tackifying resin.
2. the preparation method of modified rosin tackifying resin according to claim 1, is characterized in that the preparation method of described modified rosin tackifying resin also comprises the steps: that after obtaining modified rosin tackifying resin, add antioxidant stabilizer again in 200 ~ 230 DEG C stirs.
3. the preparation method of modified rosin tackifying resin according to claim 1, is characterized in that:
Described rosin is gum resin or toll oil rosin; Described rosin derivative is staybelite, nilox resin or resin;
Described monoterpenes compound is one or more in turps, phellandrene, kautschin, limonene, α-pinene, beta-pinene, myrcene and ocimene;
The content of the dicyclopentadiene in described dicyclopentadiene cut is 50 ~ 100wt%;
Described catalyzer is phenols sulfide:
The add-on of described dicyclopentadiene cut and the mass ratio of rosin or rosin derivative are 0.44 ~ 1.22; The add-on of described monoterpenes compound is 5 ~ 15% of formula total mass; The add-on of described catalyzer is 0.1 ~ 0.5% of rosin or rosin derivative amount;
The method of described removing low-boiling point material is flash evaporation.
4. the preparation method of modified rosin tackifying resin according to claim 3, is characterized in that:
The content of the dicyclopentadiene in described dicyclopentadiene monomer is 75 ~ 98wt%;
Described catalyzer is the phenols sulfide with following structure:
Wherein, x=1,2 or 3; Y is the integer between 0 ~ 100; R is hydrocarbon group.
5. the preparation method of modified rosin tackifying resin according to claim 4, is characterized in that: described catalyzer is the ROSINOX of 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol), French Arkema
tM, VULTAC 2, the ETHANOX 323 of Albemarle Corporation of the U.S. or the GY-323 of Guangzhou synthetic materials institute.
6. the preparation method of modified rosin tackifying resin according to claim 2, it is characterized in that: described antioxidant stabilizer is 2, 6-di-tert-butyl-4-methy phenol, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2, 2'-methylene-bis (4-methyl-6-tert-butylphenol), β-(4-hydroxy phenyl-3, 5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, 2'-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate] at least one and tricresyl phosphite (nonyl phenyl ester), three (2, 4-di-tert-butyl-phenyl) at least one in phosphorous acid ester and triphenyl phosphite, the add-on of antioxidant stabilizer is 0.2 ~ 0.5% of rosin or rosin derivative amount.
7. the preparation method of modified rosin tackifying resin according to claim 6, it is characterized in that: described antioxidant stabilizer is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) mixture of phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid is 0.6 ~ 3:1.
8. a modified rosin tackifying resin, is characterized in that: prepared by the preparation method described in any one of claim 1 ~ 7.
9. the application of modified rosin tackifying resin according to claim 8 in tackiness agent, paint of coating or ink area.
10. application according to claim 9, is characterized in that: the described application of modified rosin tackifying resin in metallocene catalyzed polyolefin adhesive area.
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| CN104558019B (en) * | 2014-12-24 | 2016-08-17 | 广西科茂林化有限公司 | A kind of Halogen abietyl fire retardant and preparation method thereof |
| CN104788617B (en) * | 2015-04-09 | 2018-06-22 | 沈阳 | A kind of method for reducing cyclopentadiene petroleum resin color number |
| CN105585961B (en) * | 2016-03-10 | 2019-06-25 | 广东科茂林产化工股份有限公司 | A kind of hydrogenation modification rosin tackifying resin and preparation method thereof |
| CN106590472B (en) * | 2016-12-08 | 2018-06-29 | 桂林森泰林化技术有限公司 | A kind of preparation method of imitative hydrogenated rosin resin hot melt adhesive |
| EP3601434B1 (en) | 2017-03-29 | 2023-01-18 | Dow Global Technologies LLC | Adhesive composition |
| CN106928854A (en) * | 2017-04-27 | 2017-07-07 | 王再青 | A kind of preparation method of modified rosin resin |
| CN107345116A (en) * | 2017-06-21 | 2017-11-14 | 广东科茂林产化工股份有限公司 | A kind of modified rosin tackifying resin and preparation method and application |
| KR102388265B1 (en) | 2017-08-24 | 2022-04-20 | 다우 글로벌 테크놀로지스 엘엘씨 | adhesive composition |
| CN114080407B (en) * | 2020-09-25 | 2024-03-08 | 爱天思株式会社 | Rosin-modified phenolic resin, lithographic ink and printed matter |
| CN114907570B (en) * | 2021-02-09 | 2024-02-13 | 济南圣泉集团股份有限公司 | Tear-resistant resin, preparation method thereof and rubber composition containing resin |
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