CN105585961A - Hydrogenated modified rosin tackifying resin and preparation method thereof - Google Patents
Hydrogenated modified rosin tackifying resin and preparation method thereof Download PDFInfo
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- CN105585961A CN105585961A CN201610137768.2A CN201610137768A CN105585961A CN 105585961 A CN105585961 A CN 105585961A CN 201610137768 A CN201610137768 A CN 201610137768A CN 105585961 A CN105585961 A CN 105585961A
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- 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; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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- 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
Abstract
The invention discloses a preparation method of hydrogenated modified rosin tackifying resin. The preparation method includes the following steps that modified rosin resin and a solvent are put in a high-pressure kettle, heating for dissolution is conducted, and a catalyst is added; the high-pressure kettle is vaccumized, nitrogen is used for replacing air in the kettle, and hydrogen is charged; a high-pressure kettle heating system and stirring system are started, the temperature is raised to 180-260 DEG C, fresh hydrogen is supplemented continuously, the pressure of hydrogen in the kettle is kept at 5-15 MPa, and a reaction is conducted for 1-4 hours; heating is stopped, the temperature is decreased, discharged material filtering are conducted, and the solvent, low-boiling-point matter and a residual solvent are removed. According to the method, through hydrogenation modification, the unsaturation degree of the resin is greatly reduced, and adhesiveness, stability and other performance are improved. Meanwhile, the invention provides the hydrogenated modified rosin tackifying resin. The hydrogenated modified rosin tackifying resin is colorless, tasteless, low in softening point, good in compatibility and capable of being widely applied to the fields of adhesives, coatings, paint, printing ink and the like.
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 pineFragrant tackifying resin and preparation method thereof.
Background technology
China's pine tree aboundresources, its rosin producing is the most important product of China's chemistry of forest product industry, alsoIt is pillar industry. Abietic resin is by rosin or modified rosin and alcohol or other material modified reaction and obtainResin, this resin has been widely used in PUR, pressure sensitive adhesive, footwear glue, multiple film glue, fluid sealant; RosinEster can also be made the modifier of rubber and plastics.
Abietic resin and Petropols are all one of gluing primary raw materials that connects field, abietic resin, oil treeFat is to use in gluing product the inside as " tackifying resin ", increases just and glues, and improves wetting and plasticity, shortEnter mixing of filler and polymer. All can use in most gluing product the inside. Both purposes are phase substantiallySeemingly, aspect of performance analysis, the tack of abietic resin is better, and the ageing-resistant aspect of Petropols also has moreGood performance. So a lot of products are all that both are used together, can neutralize both advantages, make to produceProduct performance is more perfect.
Tradition abietic resin, Petropols are due to the micro-Huang of outward appearance or brown, and with penetrating odor, veryIn large degree, limit their application.
In technical matters innovation, although have oil modified rosin resin, make resin have concurrently abietic resin withBoth advantages of Petropols, but still owing to there being a large amount of unsaturated bonds in resin, resin color,There is larger deficiency in performance ageing-resistant, compatibility aspect, can not meet Vehicles Collected from Market technical requirement.
For dicyclic pentylene modified abietic resin, a kind of method is proposed in patent CN188728A. Its toolThe preparation method of body is: the molal quantity ratio of 21 dicyclopentadienes: rosin=1:0.5-2, and at 240-260 DEG C,Under 0.5-1.3Mpa pressure, reaction 6-10 hour, then decompression, distills out low cut and makes dicyclopentadieneModified rosin resin product. The product colour making is 6-9, resin softening point 110-140 DEG C. The inventorAnother method proposing in patent CN201210567579.0. Its concrete preparation method is: toward highPress in still, add rosin or rosin derivative, monoterpenes compound, dicyclopentadiene cut and catalyst,Mix, go out air with nitrogen or carbon dioxide replacement, then pressure 0.2～0.6Mpa, temperature 170～At 290 DEG C, react 1～30 hour, reaction finishes rear decompress(ion), removes low-boiling point material, is cooled to 200～230 DEG CObtain modified rosin tackifying resin, product colour Wei≤6 that make, Suan Zhi≤70mgKOH/g, resin is softeningPoint 85-115 DEG C.
Adopt above method to produce dicyclic pentylene modified abietic resin, mainly contain following shortcoming: the one,When production, pressure is large, high to equipment requirement; The 2nd, product colour is dark, can only be applied to ink etc. color is wantedAsk low place, at adhesive area, now more and more higher to the color requirement of resin, color of resin 6-9Number look has limited its application in this field; The 3rd, resin unsaturated bond is many, and poor heat stability, at glueApplication in stick is also restricted.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part and a kind of hydrogenation modification rosin is providedTackifying resin. Meanwhile, the present invention also provides the preparation method of hydrogenation modification rosin tackifying resin described above.
For achieving the above object, the technical scheme that the present invention takes is: a kind of hydrogenation modification rosin tackifying resinPreparation method, said method comprising the steps of:
(1) modified rosin resin, solvent are dropped in autoclave, heating for dissolving, and then catalyst is addedEnter in autoclave;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 180-260 DEG C, and constantly supplement freshHydrogen, keeps Hydrogen Vapor Pressure in still at 5-15MPa, to react 1-4 hour;
(4) after reaction finishes, stop heating, open cooling system cooling, emptying pressure release, discharging is filtered,Distillation, except desolventizing, low-boiling point material, residual solvent, obtains hydrogenation modification rosin tackifying resin.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described inIn step (1), the mass ratio of modified rosin resin and modified rosin resin and solvent gross mass is 30%～60%.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described inSolvent in step (1) is at least one in pinane, 200# solvent naphtha, cyclohexane, normal heptane.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described stepSuddenly the catalyst in (1) is load type palladium series catalysts or load-type nickel series catalysts.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described negativeCarry in type palladium series catalyst, the quality percentage composition of palladium is 1～5%, and carrier is active carbon, SiO2、Al2O3Or Al2O3-SiO2; In described load-type nickel series catalysts, the quality percentage composition of nickel is 35～70%, carriesBody is active carbon, SiO2、Al2O3Or Al2O3-SiO2. As hydrogenation modification rosin tackify of the present inventionThe preparation method's of resin preferred embodiment, the catalyst adopting in described step (1) can be for example ShanD5H1A, the D5-Al of Xi Ruike new material limited company2O3Or be that the triumphant chemical science and technology of upper Hisoon is limitedAt least one in SN-5000P, SN-6000P, SN-6900P, the SN-7000P etc. of company.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described inWhen the catalyst adopting in step (1) is load type palladium series catalysts, described catalyst and modified rosin resinMass ratio be 0.5%～2.0%; When the catalyst adopting in described step (1) is load-type nickel series catalysts,The mass ratio of described catalyst and modified rosin resin is 3.0%～10.0%.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described stepSuddenly in (1), modified rosin resin and solvent are dropped into after autoclave, be heated to 100～150 DEG C of dissolvings.
As the preparation method's of hydrogenation modification rosin tackifying resin of the present invention preferred embodiment, described stepSuddenly in (4), open cooling system and cool to below 130 DEG C, adopt 180-230 DEG C of distillation except desolventizing, 230 DEG CVacuum decompression distillation removes low-boiling point material and residual solvent for 0.5～2 hour.
As the preferred embodiment of hydrogenation modification rosin tackifying resin of the present invention, described step (1)In modified rosin resin adopt with the following method and be prepared from: in autoclave, add rosin or rosin derivativeThing, monoterpenes compound and dicyclopentadiene cut, mix, with nitrogen or carbon dioxide replacement clearancenGas, then at pressure 0.2-0.6Mpa, reacts 1-30 hour at temperature 170-290 DEG C, and reaction finishes rear solutionPress, remove low-boiling point material, obtain modified rosin tackifying resin. Modified rosin resin described in the applicationPreparation method is compared with method in CN201210567579.0, except not containing side in CN201210567579.0Outside catalyst in method, rest materials and condition are all identical. The preparation method of modified rosin resin described aboveIn, preferably, described rosin is gum rosin or wood rosin; Described rosin derivative is Foral, disproportionationRosin or resin.
Preferably, described monoterpenes compound be turpentine oil, phellandrene, dipentene, citrene, australene,At least one in nopinene, laurene and ocimenum, can make the adding of described monoterpenes compound resin withMetallocene catalyzed polyolefin compatibility significantly improves.
Preferably, in described dicyclopentadiene cut, the content of dicyclopentadiene is 50～100wt%; More excellentSelection of land, in described dicyclopentadiene cut, the content of dicyclopentadiene is 75～98wt%, dicyclopentadiene heats up in a steamerDivide from petroleum cracking ethylene by-product thing processed, coal oil refining byproduct or other approach and obtain.
Preferably, the mass ratio of the addition of described dicyclopentadiene cut and rosin or rosin derivative is0.44～1.22; The addition of described monoterpenes compound is formula gross mass (rosin or rosin derivative, listThe quality of terpenoid, dicyclopentadiene cut and catalyst and) 0～15%.
The method of removing low-boiling point material preferably, is flash evaporation.
The point of the modified rosin resin that said method prepares is 80～110 DEG C, and acid number is 15～70MgKOH/g, color is less than Ghana's look number No. 16 looks.
Preferably, for making described modified rosin resin in the application of preparing in dehydrogenation modified rosin tackifying resinBetter effects if, the modified rosin resin that method described above prepares also adds antioxidant stabilizer, thenBe used further to the preparation of subsequent hydrogenation modified rosin tackifying resin. Specifically antioxidant stabilizer is joined to modification pineIn botany bar gum, stir and evenly mix the preparation that can be used for subsequent hydrogenation modified rosin tackifying resin. Described antioxygen is steadyThe addition of determining agent be in modified rosin resin preparation process rosin or rosin derivative quality 0.2～0.5%.Described antioxidant stabilizer is preferably 2,6-di-tert-butyl-4-methy phenol, four [β-(3,5-di-t-butyl-4-Hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), β-(4-hydroxylBase phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2,2 '-thiobis [3-(3,5-di-t-butyl-4-Hydroxy phenyl) ethyl propionate] at least one and tricresyl phosphite (nonyl phenyl ester), three (2,4-di-t-butylsPhenyl) at least one mixture in phosphite ester and triphenyl phosphite, but be not limited to above-mentioned changeCompound; Preferred, described antioxidant stabilizer is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid]The mixture of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphite ester, four [β-(tertiary fourths of 3,5-bis-Base-4-hydroxy phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid is excellentElect 0.6～3:1 as.
In addition, the present invention also provides a kind of hydrogenation modification rosin tackifying resin, described hydrogenation modification rosin tackify treeFat adopts method described above to prepare.
As the preferred embodiment of hydrogenation modification rosin tackifying resin of the present invention, described hydrogenation modification pineThe softening point of fragrant tackifying resin is 80～110 DEG C, and acid number is 15～70mgKOH/g, and color is less than Ghana's look numberNo. 1 look.
Hydrogenation modification rosin tackifying resin unsaturated bond of the present invention obviously reduces, and has more excellent ageing-resistantStability, softening point is lower, compatibility is better, color is better, can be widely used in adhesive, coating oilThe fields, the particularly application in metallocene catalyzed polyolefin adhesive area such as paint, ink.
The beneficial effect of hydrogenation modification rosin tackifying resin of the present invention is:
(1) the present invention prepares hydrogenation modification rosin tackifying resin and sets with respect to unhydrided dicyclo modified rosinFat, unsaturated bond obviously reduces, and resin has more excellent ageing-resistant stability.
(2) the hydrogenation modification rosin tackifying resin softening point 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. 1 look, and the dicyclo modified rosin resin of tradition invention is softeningPoint is 110～140 DEG C, and acid number is 5～30mgKOH/g, and color Ghana look number 6～No. 9 looks, due to thisBright resin softening point is lower, and compatibility is better, and color is better, and therefore application is extensive, can be applied toThe fields such as adhesive, paint of coating and ink.
(3) the hydrogenation modification rosin tackifying resin that prepared by the present invention and traditional ester gum, rosin season pentaTetrol ester, dicyclo amylene resin and Abietyl modified dicyclo amylene resin-phase ratio, resin of the present invention and metallocene are urgedChange compatible polyolefin good, changed present stage abietic resin, dicyclo amylene resin and Abietyl modified dicyclo pentaOlefine resin can not be applied the present situation with metallocene catalyzed polyolefin.
(4) the hydrogenation modification rosin tackifying resin that prepared by the present invention, because rosin contains carboxyl polar group,Make the PUR ratio terpene resin with this resin preparation, the heat of C5 Petropols preparation under equal formulaThe non-polar materials such as melten gel and PP, PET have better wetability and adhesive force.
The preparation method of hydrogenation modification rosin tackifying resin of the present invention, by hydrogenation modification, makes resin insatiable hungerGreatly reduce with degree, the performances such as cohesive, stability all increase. The method of the invention system of employingThe standby hydrogenation modification rosin tackifying resin obtaining, colourless, tasteless, softening point is low, compatibility good, can be extensivelyBe applied to the fields such as adhesive, paint of coating, ink.
Detailed description of the invention
For the object, technical solutions and advantages of the present invention are better described, below in conjunction with specific embodiment pairThe present invention is described further.
The D5H1A, the D5-Al that in embodiment, select2O3Purchased 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, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, pinane are dropped in 1L autoclave, be heated to 100-150 DEG C of dissolving, soAfter again catalyst D5H1A is added in autoclave; Wherein modified rosin resin and modified rosin resin and pinaneThe mass ratio of gross mass is 30%, and the mass ratio of catalyst and modified rosin resin is 1.0%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 260 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 10MPa, to react 4 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 130 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is that 80 DEG C, acid number are34.2 (mgKOH/g), color are Ghana's look 9.5, adopt with the following method and are prepared from: be 1L toward volumeIn autoclave, add the dicyclopentadiene cut of resin, dicyclopentadiene content 75wt%, whereinThe addition of described dicyclopentadiene cut and the mass ratio of resin are to be warming up in 0.75,2 hour265 DEG C, pressure is 0.60Mpa, react 2 hours, and decompress(ion), low-boiling point material is removed in flash distillation, then coolingTo 220 DEG C, obtain modified rosin tackifying resin. The resin of selecting in embodiment, acid number 181(mgKOH/g), 80.6 DEG C of softening points, being dissolved in Ghana's look that toluene is made into 50% solution is 2+.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 90 DEG C, and acid number is 31.5(mgKOH/g), color is Ghana look < 1.
Embodiment 2
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, pinane are dropped in 1L autoclave, be heated to 100-150 DEG C of dissolving, soAfter again catalyst D5H1A is added in autoclave; Wherein modified rosin resin and modified rosin resin and pinaneThe mass ratio of gross mass is 38.5%, and the mass ratio of catalyst and modified rosin resin is 2.0%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 240 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 15MPa, to react 3 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 105 DEG C, and acid number is 15(mgKOH/g), color is Ghana look 10+, adopts with the following method and is prepared from: the high pressure that is 1L toward volumeIn reactor, add the dicyclopentadiene cut of resin, turpentine oil and dicyclopentadiene content 98wt%, itsDescribed in the addition of dicyclopentadiene cut and the mass ratio of resin be 1.12, described terebinthine addingAmount is 1%, 2 hour of formula gross mass (quality of resin, turpentine oil and dicyclopentadiene cut and)Inside be warming up to 290 DEG C, pressure is 0.55Mpa, react 1.0 hours, and decompress(ion), low-boiling point material is removed in flash distillation,Then cool to 200 DEG C, obtain modified rosin tackifying resin.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 100 DEG C, and acid number is19.2 (mgKOH/g), color is Ghana look < 1.
Embodiment 3
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, normal heptane are dropped in 1L autoclave, are heated to 100-150 DEG C of dissolving,And then catalyst S N-7000P is added in autoclave; Wherein modified rosin resin and modified rosin resin andThe mass ratio of normal heptane gross mass is 60.0%, and the mass ratio of catalyst and modified rosin resin is 7%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 220 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 8MPa, to react 3.5 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 90.2 DEG C, and acid number is60.5 (mgKOH/g), color is Ghana's look 10, adopts with the following method and is prepared from: the height that is 1L toward volumePress the dicyclopentadiene cut that adds Foral, laurene and dicyclopentadiene content 50wt% in reactor,The addition of wherein said dicyclopentadiene cut and the mass ratio of Foral are 0.44, the adding of described laureneEnter amount for 6.9%, 2 of formula gross mass (quality of Foral, laurene and dicyclopentadiene cut and)In hour, be warming up to 220 DEG C, pressure is 0.58Mpa, react 4.0 hours, and decompress(ion), low boilers is removed in flash distillationMatter, then cools to 205 DEG C, obtains modified rosin tackifying resin.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 84.3 DEG C, and acid number is66.5 (mgKOH/g), color is Ghana look < 1.
Embodiment 4
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, 200# solvent naphtha are dropped in 1L autoclave, be heated to 100-150 DEG C moltenSeparate, and then catalyst S N-5000P is added in autoclave; Wherein modified rosin resin and modified rosin treeThe mass ratio of fat and 200# solvent naphtha gross mass is 50.0%, and the mass ratio of catalyst and modified rosin resin is10.0％；
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 180 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 5MPa, to react 1 hour;
(4) after reaction finishes, stop heating, open cooling system and cool to 110 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 110 DEG C, and acid number is 70.0(mgKOH/g), color is Ghana look 11+, adopts method as described below to be prepared from: be 1L toward volumeIn autoclave, add the dicyclopentadiene cut of gum rosin, dicyclopentadiene alkene and dicyclopentadiene content 83wt%,The addition of wherein said dicyclopentadiene cut and the mass ratio of gum rosin are 1.22; Adding of described dicyclopentadiene alkeneIn 5%, 2 hour that amount is formula gross mass (quality of gum rosin, dicyclopentadiene alkene and dicyclopentadiene cut and)Be warming up to 170 DEG C, pressure is 0.20Mpa, react 30.0 hours, and decompress(ion), low-boiling point material is removed in flash distillation,Then cool to 230 DEG C, obtain modified rosin tackifying resin. In the present embodiment modified rosin resin used, also addEnter to have antioxidant stabilizer, described antioxidant stabilizer was four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] seasons pentaThe mixture of tetrol ester and three (2,4-di-tert-butyl-phenyl) phosphite ester, four [β-(3,5-di-t-butyl-4-Hydroxy phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid is 3:1,Described antioxidant stabilizer directly joins in modified rosin resin, stirs, described antioxidant stabilizerAddition is 0.2% of gum rosin quality.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 109 DEG C, and acid number is19.2 (mgKOH/g), color is Ghana look < 1.
Embodiment 5
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, normal heptane are dropped in 1L autoclave, are heated to 100-150 DEG C of dissolving,And then catalyst S N-6000P is added in autoclave; Wherein modified rosin resin and modified rosin resin andThe mass ratio of normal heptane gross mass is 60.0%, and the mass ratio of catalyst and modified rosin resin is 5%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 240 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 12MPa, to react 1.5 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 85.5 DEG C, and acid number is65.5 (mgKOH/g), color is Ghana's look 10, adopts with the following method and is prepared from: the height that is 1L toward volumePress the dicyclopentadiene cut that adds disproportionated rosin, phellandrene and dicyclopentadiene content 50wt% in reactor,The addition of wherein said dicyclopentadiene cut and the mass ratio of disproportionated rosin are 0.5; Adding of described phellandreneEnter amount for 10%, 2 of formula gross mass (quality of disproportionated rosin, phellandrene and dicyclopentadiene cut and)In hour, be warming up to 250 DEG C, pressure is 0.43Mpa, react 8 hours, and decompress(ion), low boilers is removed in flash distillationMatter, then cools to 210 DEG C, obtains modified rosin tackifying resin. In the present embodiment modified rosin resin usedAlso add and have antioxidant stabilizer, described antioxidant stabilizer is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid]The mixture of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphite ester, four [β-(3,5-di-t-butyls-4-hydroxy phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid is 0.6:1,Described antioxidant stabilizer directly joins in modified rosin resin, stirs, described antioxidant stabilizerAddition is 0.5% of disproportionated rosin quality.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 83.2 DEG C, and acid number is63.2 (mgKOH/g), color is Ghana look < 1.
Embodiment 6
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) by the mixture of modified rosin resin, pinane and normal heptane (the wherein quality of pinane and normal heptaneThan being 1:1) drop in 1L autoclave, be heated to 100-150 DEG C of dissolving, and then by catalyst D5-Al2O3Add in autoclave; Wherein modified rosin resin and modified rosin resin and solvent (mixing of pinane and normal heptaneCompound) mass ratio of gross mass is 35%, the mass ratio of catalyst and modified rosin resin is 0.5%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 200 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 9MPa, to react 2.5 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 108 DEG C, and acid number is25.5 (mgKOH/g), color is Ghana's look 10, adopts with the following method and is prepared from: the height that is 1L toward volumePress mixture (the wherein mass ratio of ocimenum and laurene that adds wood rosin, ocimenum and laurene in reactorFor 1:1) and the dicyclopentadiene cut of dicyclopentadiene content 100wt%, wherein said dicyclopentadiene cutAddition and the mass ratio of wood rosin be 0.82; The addition of described phellandrene and terebinthine mixture is for joiningSide's gross mass (mixture of wood rosin, ocimenum and laurene, the quality of dicyclopentadiene cut and)In 15.0%, 2 hour, be warming up to 240 DEG C, pressure is 0.60Mpa, react 15 hours, and decompress(ion), flash distillation is removedLow-boiling point material, then cools to 210 DEG C, obtains modified rosin tackifying resin.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 105 DEG C, and acid number is23.6 (mgKOH/g), color is Ghana look < 1.
Embodiment 7
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) by the mixture of modified rosin resin cyclohexane and normal heptane (the wherein quality of pinane and normal heptaneThan being 1:1.5) drop in 1L autoclave, be heated to 100-150 DEG C of dissolving, and then by catalyst S N-6900PAdd in autoclave; Wherein modified rosin resin and modified rosin resin and solvent (cyclohexane and normal heptaneMixture) mass ratio of gross mass is 40%, the mass ratio of catalyst and modified rosin resin is 3.0%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 210 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 6MPa, to react 4 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 80.5 DEG C, and acid number is69.5 (mgKOH/g), color is Ghana's look 9, adopts with the following method and is prepared from: the height that is 1L toward volumePress mixture (the wherein matter of citrene and australene that adds resin, citrene and australene in reactorAmount is than for 1:2), the dicyclopentadiene cut of dicyclopentadiene content 70wt%, wherein said dicyclopentadiene heats up in a steamerThe addition of dividing and the mass ratio of resin are 0.6; The addition of the mixture of described citrene and australeneFor formula gross mass (mixture of resin, citrene and australene, the quality of dicyclopentadiene cut and)8%, 2 hour in be warming up to 265 DEG C, pressure is 0.45Mpa, react 15 hours, decompress(ion), flash distillation is removedLow-boiling point material, then cools to 200 DEG C, obtains modified rosin tackifying resin.
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 79 DEG C, and acid number is 65.2(mgKOH/g), color is Ghana look < 1.
Embodiment 8
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogen described in the present embodimentChanging modified rosin tackifying resin adopts following methods to be prepared from:
(1) modified rosin resin, cyclohexane are dropped in 1L autoclave, are heated to 100-150 DEG C of dissolving,And then by palladium catalyst D5-Al2O3Add in autoclave; Wherein modified rosin resin and modified rosin resinWith the mass ratio of cyclohexane gross mass be 45%, the mass ratio of catalyst and modified rosin resin is 0.8%;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 230 DEG C, and constantly supplement fresh hydrogenGas, keeps Hydrogen Vapor Pressure in still at 7MPa, to react 2 hours;
(4) after reaction finishes, stop heating, open cooling system and cool to 120 DEG C, emptying pressure release, goes outMaterial filters, and filtrate enters boiler, and 180-230 DEG C of distillation removes desolventizing, then adopts 230 DEG C of vacuum decompressions to steamHeat up in a steamer 0.5-2 hour, remove low-boiling point material, residual solvent, obtain hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin adopting in step described in the present embodiment (1) is 101 DEG C, and acid number is23.5 (mgKOH/g), color is Ghana's look 11, adopts with the following method and is prepared from: the height that is 1L toward volumePress the dicyclopentadiene cut that adds gum rosin, nopinene and dicyclopentadiene content 93wt% in reactor, itsDescribed in the addition of dicyclopentadiene cut and the mass ratio of gum rosin be 1.02, the addition of described nopineneFor 12%, 2 hour of formula gross mass (quality of gum rosin, nopinene and dicyclopentadiene cut and)Inside be warming up to 200 DEG C, pressure is 0.32Mpa, react 20 hours, and decompress(ion), low-boiling point material is removed in flash distillation,Then cool to 220 DEG C, obtain modified rosin tackifying resin. .
After testing, the softening point of the present embodiment gained hydrogenation modification rosin tackifying resin is 100 DEG C, and acid number is22 (mgKOH/g), color is Ghana look < 1.
The last above embodiment that it should be noted that of institute is only in order to technical scheme of the present invention to be described but not to thisThe restriction of invention protection domain, although the present invention is explained in detail with reference to preferred embodiment, this areaThose of ordinary skill should be appreciated that and can modify or be equal to replacement technical scheme of the present invention, andDo not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a preparation method for hydrogenation modification rosin tackifying resin, is characterized in that, described method comprise withLower step:
(1) modified rosin resin, solvent are dropped in autoclave, heating for dissolving, and then catalyst is addedEnter in autoclave;
(2) autoclave is vacuumized, with air in nitrogen replacement still, then be filled with hydrogen, regulate hydrogen in stillPressure;
(3) start autoclave heating system and stirring system, be warmed up to 180-260 DEG C, and constantly supplement freshHydrogen, keeps Hydrogen Vapor Pressure in still at 5-15MPa, to react 1-4 hour;
(4) after reaction finishes, stop heating, open cooling system cooling, emptying pressure release, discharging is filtered,Distillation, except desolventizing, low-boiling point material, residual solvent, obtains hydrogenation modification rosin tackifying resin.
2. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 1, is characterized in that,In described step (1), the mass ratio of modified rosin resin and modified rosin resin and solvent gross mass is30％～60％。
3. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 1 or 2, its feature existsBe at least one in pinane, 200# solvent naphtha, cyclohexane, normal heptane in, the solvent in described step (1)Kind.
4. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 1, is characterized in that,Catalyst in described step (1) is load type palladium series catalysts or load-type nickel series catalysts.
5. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 4, is characterized in that,In described load type palladium series catalysts, the quality percentage composition of palladium is 1～5%, and carrier is active carbon, SiO2、Al2O3Or Al2O3-SiO2; In described load-type nickel series catalysts, the quality percentage composition of nickel is 35～70%,Carrier is active carbon, SiO2、Al2O3Or Al2O3-SiO2。
6. the preparation method of the hydrogenation modification rosin tackifying resin as described in claim 4 or 5, its feature existsIn, when the catalyst adopting in described step (1) is load type palladium series catalysts, described catalyst and modificationThe mass ratio of abietic resin is 0.5%～2.0%; The catalyst adopting in described step (1) is load-type nickel systemWhen catalyst, the mass ratio of described catalyst and modified rosin resin is 3.0%～10.0%.
7. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 1, is characterized in that,In described step (1), modified rosin resin and solvent are dropped into after autoclave, be heated to 100～150 DEG C of dissolvings.
8. the preparation method of hydrogenation modification rosin tackifying resin as claimed in claim 1, is characterized in that,In described step (4), open cooling system and cool to below 130 DEG C, adopt 180-230 DEG C of distillation except desolventizing,230 DEG C of vacuum decompression distillations remove low-boiling point material and residual solvent for 0.5～2 hour.
9. the hydrogenation modification rosin tackify that employing method as described in claim 1～8 any one preparesResin.
10. hydrogenation modification rosin tackifying resin as claimed in claim 9, is characterized in that, described hydrogenation changesThe softening point of property rosin tackifying resin is 80～110 DEG C, and acid number is 15～70mgKOH/g, and color is less than GhanaLook number No. 1 look.
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| KR20190126010A (en) * | 2017-03-29 | 2019-11-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Adhesive composition |
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| KR102302416B1 (en) | 2017-03-29 | 2021-09-15 | 다우 글로벌 테크놀로지스 엘엘씨 | adhesive composition |
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| US11326046B2 (en) | 2017-03-29 | 2022-05-10 | Dow Global Technologies Llc | Adhesive composition |
| CN110431181B (en) * | 2017-03-29 | 2023-01-24 | 陶氏环球技术有限责任公司 | Adhesive composition |
| WO2019037039A1 (en) | 2017-08-24 | 2019-02-28 | Dow Global Technologies Llc | Adhesive composition |
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| CN114574104A (en) * | 2022-03-18 | 2022-06-03 | 广西科茂林化有限公司 | Ultraviolet light cured rosin resin and preparation method and application thereof |
| CN114574104B (en) * | 2022-03-18 | 2023-12-19 | 广西科茂林化有限公司 | Ultraviolet light cured rosin resin and preparation method and application thereof |
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