CN1887928A - Dicyclopentadiene-rosin polymer and its prepn and application - Google Patents
Dicyclopentadiene-rosin polymer and its prepn and application Download PDFInfo
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- CN1887928A CN1887928A CN 200610012862 CN200610012862A CN1887928A CN 1887928 A CN1887928 A CN 1887928A CN 200610012862 CN200610012862 CN 200610012862 CN 200610012862 A CN200610012862 A CN 200610012862A CN 1887928 A CN1887928 A CN 1887928A
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- dicyclopentadiene
- rosin
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- rosin polymer
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Abstract
The dicyclopentadiene-rosin polymer is prepared through heat polymerizing dicyclopentadiene and rosin, and has softening point of 110-140 deg.c, acid value 5-30 mgKOH/g, colorimetric number not greater than 9, and weight average molecular weight 3000-6000. after being dissolved in 2 time weight of flax seed oil, the solution has viscosity of 200-600 mPa .s at 25 deg.c. The present invention also provides the preparation process of the dicyclopentadiene-rosin polymer. The dicyclopentadiene-rosin polymer may find its wide application in ink, paint, adhesive, etc.
Description
Technical field
The present invention relates to a kind of dicyclopentadiene-rosin polymer, its preparation method, and in the application of printing ink, coating, adhesive area.
Background technology
From petroleum cracking system ethylene by-product C
5Cut extracts dicyclopentadiene (DCPD) in the coal oil refining by-product light benzene cut, can be used for preparing dcpd resin.Dcpd resin is the relatively low thermoplastic hydrocarbon resin of a kind of weight-average molecular weight, molecular weight Mw=1000～5000,90～130 ℃ of softening temperatures, color and luster is more shallow, can be dissolved in organic solvents such as benzene class, but dcpd resin can not be directly used in the preparation of printing ink, coating, tackiness agent, and its reason is as follows:
1, dcpd resin contains a large amount of unsaturated link(age)s, and thermostability is relatively poor, and oxidative stability is lower, storing, continuing reaction when using easily, causes resin poorly soluble in organic solvent, and is poor with the consistency of other resins.
2, dcpd resin and hydrogenated products thereof polar functionalities not is poor with the binding ability of pigment, mineral filler in use, the printing ink of preparation, coating, tackiness agent poor adhesive force.
Therefore, dcpd resin must be carried out chemical modification after, just can be used for manufacturings such as printing ink, coating, tackiness agent.
To dcpd resin carry out chemical modification commonly used two kinds of methods are arranged, the one, hydrogenation modification, another kind are with vinylformic acid or maleic acid dicyclopentadiene to be carried out graft modification, to improve the acid number of resin.These two kinds of methods all are in order to reduce the content of dicyclopentadiene unsaturated link(age), to reach the acid number that improves petroleum resin and propose.
Yet above-mentioned two kinds of method of modifying weak points are a lot, particularly:
1, how many reactions the preparation of the hydrogenation modification of dicyclopentadiene need need be carried out and just can obtain product, preparation cost height with precious metals such as nickel, palladium, platinum, rhenium, rutheniums as hydrogenation catalyst.
2, the dcpd resin color of modification is darker, makes resin be subjected to very big restriction in production application.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned defective, provide a kind of rosin that adopts dicyclopentadiene to be carried out the dicyclopentadiene-rosin polymer that obtains after the modification.
Another object of the present invention provides a kind of preparation method of dicyclopentadiene-rosin polymer.
A further object of the invention provides the application of dicyclopentadiene-rosin polymer.
Dicyclopentadiene-rosin polymer provided by the invention is to be made by dicyclopentadiene cut and rosin thermopolymerization.The softening temperature of this dicyclopentadiene-rosin polymer is 110 ℃～140 ℃; Acid number 5～30mgKOH/g; Jia Shi colorimetric number≤9.With this dicyclopentadiene-rosin polymer and oleum lini according to 1: 2 weight ratio dissolving after, be 200～600mPas at the viscosity of 25 ℃ of mensuration.
The structure of the dicyclopentadiene-rosin polymer that the present invention makes can characterize by the infrared spectra collection of illustrative plates.
Wherein, the charateristic avsorption band of one of raw material dicyclopentadiene is:
Unsaturated double-bond C-H stretching vibration absorption peak 3045.8cm
-1Saturated alkyl C-H stretching vibration absorption peak 2963～2800cm
-1Unsaturated double-bond C=C stretching vibration absorption peak 1680～1620cm
-1C-H formation vibration absorption peak 1470～1300cm
-1
Two rosiny charateristic avsorption bands of raw material are:
Unsaturated double-bond C-H stretching vibration absorption peak, saturated alkyl C-H stretching vibration absorption peak and carboxyl-COOH absorption peak are all at 2700～3600cm
-1The place is typical case's performance of carboxyl absorption peak at the wide absorption peak in this place; The C=O stretching vibration absorption peak of unsaturated double-bond C=C stretching vibration absorption peak and carboxyl is superimposed in 1693.5cm
-1The place; C-H formation vibration absorption peak is then at 1459～1200cm
-1The place shows a plurality of absorption peaks.
The product feature peak of the dicyclopentadiene-rosin polymer that the present invention makes then shows as:
At first, 2700～3600cm
-1The wide carboxyl absorption peak at place has disappeared, at 2928cm
-1The place has shown C-H stretching vibration absorption peak; And 1719cm
-1The place then is the absorption peak of C=O stretching vibration in the ester group, and C-O-C stretching vibration absorption peak corresponding with it then appears at 1146cm
-1And 1244cm
-1The place; The unsaturated double-bond C=C stretching vibration absorption peak that does not wherein have to change then appears at 1696cm
-1The place.
The present invention also provides a kind of method for preparing dicyclopentadiene-rosin polymer.This method is to be formed by dicyclopentadiene cut and rosin thermopolymerization, its concrete preparation method is according to dicyclopentadiene: the molal quantity ratio of rosin=1: 0.5～2, the dicyclopentadiene cut is mixed with rosin, at 240～260 ℃, 0.5 react 6～10h under the～1.3MPa condition, be decompressed to 0.08Mpa, make polymeric articles after steaming low cut.
The dicyclopentadiene cut that is used for the inventive method is from petroleum cracking system ethylene by-product C
5Cut extracts in the coal oil refining by-product light benzene cut, and what are little to the influence of polymeric articles for its content, and the yield of polymkeric substance, softening temperature, acid number are all less than too big variation.Just when the content of dicyclopentadiene cut was lower than 65%, the softening temperature of polymeric articles obviously reduced, and acid number also increases.Therefore, the dicyclopentadiene cut content of the present invention's use is 65～98%.
The present invention can also add the fumaric acid and/or the maleic acid that account for rosin weight 1～3% when the preparation dicyclopentadiene-rosin polymer.The unsaturated link(age) that contains in fumaric acid and/or the maleic acid has participated in the polyreaction of rosin and dicyclopentadiene, thereby in the polymer molecule side chain, introduce carboxyl, increase the content of polymer molecular structure Semi-polarity group, can further improve the solubility property of polymeric articles.Under the certain situation of rosin and dicyclopentadiene consumption, add 1～3% fumaric acid and/or maleic acid, the polymeric articles acid number that obtains is higher relatively.
By selecting dicyclopentadiene and rosiny different ratios, can prepare the polymeric articles of different softening point, different acid numbers.Dicyclopentadiene compares greater than 1 with the rosiny molal quantity, and the acid number of polymeric articles is low, softening temperature is high, colourity is shallow; The molal quantity ratio is less than 1, and the softening temperature of polymeric articles is low, the acid number height.
Weight-average molecular weight Mw=3000～6000 of the dicyclopentadiene-rosin polymer that obtains with aforesaid method have very wide variation range.Number-average molecular weight of the present invention is to adopt gel permeation chromatography (GPC), is standard with the polystyrene, measures under chloroform moving phase.
The present invention is by synthesizing dicyclopentadiene-rosin polymer with dicyclopentadiene and rosin thermopolymerization, the structure of rosin and dicyclopentadiene is introduced in the same molecular structure of polymkeric substance, make polymeric articles have that softening temperature height, acid number are moderate, the characteristics of lighter color, aromatic hydrocarbons, aliphatic solvents had both been dissolved in, also dissolve in oleum lini isopolarity solvent, satisfied the different service requirementss of printing ink, coating, tackiness agent.
Following table is that the technical indicator of polymeric articles of the present invention and similar products at home and abroad compares.
| Softening temperature, ℃ | Jia Shi is than colourity, number | Acid number, mgKOH/g | |
| Polymkeric substance of the present invention | 110～140 | ≤9 | 5～30 |
| Terpine resin | 80～110 | ≤9 | ≤0.5 |
| C 5Petroleum resin | 90～110 | ≤9 | ≤0.5 |
| C 9Petroleum resin | 100～120 | 10～18 | ≤0.5 |
| Dcpd resin | 90～120 | ≤14 | ≤0.5 |
| Rosin glycerine (tetramethylolmethane) ester | 80～120 | ≤10 | ≤18 |
As can be seen from the above table, the technical indicator of product of the present invention is close with other like products, and the part technical indicator is better than other products, can be widely used in fields such as printing ink, coating, tackiness agent.
Dicyclopentadiene-rosin polymer of the present invention can be used as ink adhesive and uses, and uses in base gravure ink, web offset printing ink, and effect is better than common terpine resin, petroleum resin, ester gum and pentalyn.
125～135 ℃ of softening temperatures that are used for the dicyclopentadiene-rosin polymer of printing ink preparation, acid number be at 10～18mgKOH/g, Jia Shi colorimetric number≤9, and major advantage is presented as:
1, oily solubility property is good, and resin binder and the printing ink viscosity of making are very little because of temperature variation.
2, the printing ink flexibility is good, and demulsification performance is good, and printing quality is good.
3, the printing ink thixotropic property is good, and drying property is good.
Dicyclopentadiene-rosin polymer of the present invention also can be used as tackiness agent and uses with resin, right to replace-tert butyl phenolic resin (2402 resin).
125～130 ℃ of softening temperatures that are used for the dicyclopentadiene-rosin polymer of tackiness agent preparation, acid number be at 20～30mgKOH/g, Jia Shi colorimetric number≤9, and major advantage is presented as:
1, the solvability height in solvent.
2, good with the macromolecular material consistency, brushing easily.
3, the initial bonding strength of neoprene latex tackiness agent and peel strength improve greatly, and resistance toheat improves, and package stability strengthens, and resin dissolves speed and speed of response are fast.
Dicyclopentadiene-rosin polymer of the present invention can also be used as the coating lacquer sill.
110～125 ℃ of dicyclopentadiene-rosin polymer softening temperatures that are used for coating preparation, acid number be at 5～20mgKOH/g, Jia Shi colorimetric number≤9, and major advantage is presented as:
1 and the grinding wettability of mineral dye good, the package stability height of coating does not return slightly, skinning not.
2, the use flow leveling of coating is good, moderate drying speed.
3, ADHESION OF PAINTS power height, paint film mechanical property, water resistance, chemical resistance are good, and outdoor weatherability can be good.
Embodiment
Embodiment 1:
Take by weighing 408g rosin, 279g80% dicyclopentadiene cut adds in the 1L autoclave, is warming up to 160 ℃, open and stir, be warming up to 250 ℃ again, pressure reaches 1.0MPa, reacts 9.5 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 624g dicyclopentadiene-rosin polymer.
After measured, 133 ℃ of the softening temperatures of product, acid number 18mgKOH/g, Jia Shi colorimetric numbers 8, viscosity 530mPas, weight-average molecular weight Mw=5230.This product is used for printing ink, coating preparation.
Embodiment 2
Take by weighing 380g rosin, 340g70% dicyclopentadiene cut and 8.5g maleic acid, add in the 1L autoclave, be warming up to 160 ℃, open and stir, be warming up to 240 ℃ again, pressure reaches 0.9MPa, reacts 7.8 hours, is decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 609g dicyclopentadiene-rosin polymer.
After measured, 140 ℃ of the softening temperatures of product, acid number 25mgKOH/g, Jia Shi colorimetric numbers 9, viscosity 600mPas, weight-average molecular weight Mw=6000.This product is used for coating, printing ink preparation.
Embodiment 3:
Take by weighing 432g rosin, 264g65% dicyclopentadiene cut adds in the 1L autoclave, is warming up to 160 ℃, open and stir, be warming up to 260 ℃ again, pressure reaches 0.8MPa, reacts 9 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 611g dicyclopentadiene-rosin polymer.
After measured, 128 ℃ of the softening temperatures of product, acid number 19mgKOH/g, Jia Shi colorimetric numbers 7, viscosity 460mPas, weight-average molecular weight Mw=4680.This product is used for printing ink, coating preparation.
Embodiment 4
Take by weighing 472g rosin, 203g85% dicyclopentadiene cut adds in the 1L autoclave, is warming up to 160 ℃, open and stir, be warming up to 245 ℃ again, pressure reaches 0.65MPa, reacts 10 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 640g dicyclopentadiene-rosin polymer.
After measured, 120 ℃ of the softening temperatures of product, acid number 22mgKOH/g, Jia Shi colorimetric numbers 8, viscosity 380mPas, weight-average molecular weight Mw=4250.This product is used for the tackiness agent preparation.
Embodiment 5
Take by weighing 453g rosin, 147g 90% dicyclopentadiene cut, fumaric acid 6.5g adds in the 1L autoclave, be warming up to 140 ℃, open and stir, be warming up to 260 ℃ again, pressure reaches 0.53MPa, reacted 8.5 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 607g dicyclopentadiene-rosin polymer.
After measured, 123 ℃ of the softening temperatures of product, acid number 29mgKOH/g, Jia Shi colorimetric numbers 6, viscosity 290mPas, weight-average molecular weight Mw=3560.This product is used for the tackiness agent preparation.
Embodiment 6
Take by weighing 327g rosin, 379g75% dicyclopentadiene cut adds in the 1L autoclave, is warming up to 160 ℃, open and stir, be warming up to 255 ℃ again, pressure reaches 1.2MPa, reacts 9 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 602g dicyclopentadiene-rosin polymer.
After measured, 138 ℃ of the softening temperatures of product, acid number 6mgKOH/g, Jia Shi colorimetric numbers 6, viscosity 590mPas, weight-average molecular weight Mw=5830.This product is used for the coating preparation.
Embodiment 7
Take by weighing 589g rosin, 135g95% dicyclopentadiene cut adds in the 1L autoclave, is warming up to 160 ℃, open and stir, be warming up to 258 ℃ again, pressure reaches 0.35MPa, reacts 9.5 hours, be decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 711g dicyclopentadiene-rosin polymer.
After measured, 113 ℃ of the softening temperatures of product, acid number 28mgKOH/g, Jia Shi colorimetric numbers 9, viscosity 210mPas, weight-average molecular weight Mw=3140.This product is used for the tackiness agent preparation.
Embodiment 8
Take by weighing 460g rosin, 252g88% dicyclopentadiene cut and 5.3g maleic acid, add in the 1L autoclave, be warming up to 160 ℃, open and stir, be warming up to 240 ℃ again, pressure reaches 0.7Mpa, reacts 7.8 hours, is decompressed to 0.08Mpa afterwards, steam unreacted reactant, obtain the 668g dicyclopentadiene-rosin polymer.
After measured, 126 ℃ of the softening temperatures of product, acid number 18mgKOH/g, Jia Shi colorimetric numbers 9, viscosity 590mPas, weight-average molecular weight Mw=5940.This product is used for coating, printing ink preparation.
Claims (9)
1, a kind of dicyclopentadiene-rosin polymer, it is characterized in that making by dicyclopentadiene cut and rosin thermopolymerization, 110 ℃～140 ℃ of the softening temperatures of this polymkeric substance, weight-average molecular weight Mw=3000～6000, with oleum lini according to the dissolving of 1: 2 weight ratio after, 25 ℃ viscosity is 200～600mPas;
2, dicyclopentadiene-rosin polymer according to claim 1, the acid number that it is characterized in that this polymkeric substance is 5～30mgKOH/g.
3, dicyclopentadiene-rosin polymer according to claim 1 is characterized in that Jia Shi colorimetric number≤9 of this polymkeric substance.
4, the preparation method of the dicyclopentadiene-rosin polymer of claim 1, be to form by dicyclopentadiene cut and rosin thermopolymerization, it is characterized in that dicyclopentadiene and rosin according to 1: 0.5～2 molal quantity than mixing, at 240～260 ℃, 0.5 react 6～10h under the～1.3MPa condition, be decompressed to 0.08Mpa, steam low cut and make polymeric articles.
5, dicyclopentadiene-rosin polymer preparation method according to claim 4, the content that it is characterized in that described dicyclopentadiene cut is 65～98%.
6, dicyclopentadiene-rosin polymer preparation method according to claim 4 is characterized in that also adding the fumaric acid and/or the maleic acid that account for rosin weight 1%～3%.
7, claim 1 dicyclopentadiene-rosin polymer is as the application of ink adhesive.
8, claim 1 dicyclopentadiene-rosin polymer is as the application of tackiness agent with resin.
9, claim 1 dicyclopentadiene-rosin polymer is as the application of coating lacquer sill.
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| CNB2006100128621A CN100415789C (en) | 2006-06-21 | 2006-06-21 | Dicyclopentadiene-rosin polymer and its prepn and application |
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| CNB2006100128621A CN100415789C (en) | 2006-06-21 | 2006-06-21 | Dicyclopentadiene-rosin polymer and its prepn and application |
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| CN1887928A true CN1887928A (en) | 2007-01-03 |
| CN100415789C CN100415789C (en) | 2008-09-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977615A (en) * | 2012-12-25 | 2013-03-20 | 普洱科茂林化有限公司 | Modified rosin tackifying resin as well as preparation method and application thereof |
| CN105860852A (en) * | 2016-04-15 | 2016-08-17 | 梧州市飞卓林产品实业有限公司 | Preparation method of non-crystallizable rosin |
| CN112980323A (en) * | 2021-01-26 | 2021-06-18 | 广州市帝天印刷材料有限公司 | Anti-yellowing composition for duct gloss oil, anti-yellowing environment-friendly duct gloss oil and preparation method thereof |
| EP4215589A1 (en) * | 2022-01-19 | 2023-07-26 | Hubergroup Deutschland GmbH | A rosin polymer to be used as inert component in a coating, in particular a radiation curing coating such as a radiation curing printing ink |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680349A (en) * | 1985-01-14 | 1987-07-14 | Toyo Soda Manufacturing Co., Ltd. | Method of polymerizing vinyl monomers with coated reactor |
| CN1125735A (en) * | 1994-12-30 | 1996-07-03 | 梁海成 | Synethsis method of pentadiene graft copolymer |
| JP2002322450A (en) * | 2001-04-26 | 2002-11-08 | Harima Chem Inc | Resin tackifier and method for producing the same |
-
2006
- 2006-06-21 CN CNB2006100128621A patent/CN100415789C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977615A (en) * | 2012-12-25 | 2013-03-20 | 普洱科茂林化有限公司 | Modified rosin tackifying resin as well as preparation method and application thereof |
| CN105860852A (en) * | 2016-04-15 | 2016-08-17 | 梧州市飞卓林产品实业有限公司 | Preparation method of non-crystallizable rosin |
| CN112980323A (en) * | 2021-01-26 | 2021-06-18 | 广州市帝天印刷材料有限公司 | Anti-yellowing composition for duct gloss oil, anti-yellowing environment-friendly duct gloss oil and preparation method thereof |
| EP4215589A1 (en) * | 2022-01-19 | 2023-07-26 | Hubergroup Deutschland GmbH | A rosin polymer to be used as inert component in a coating, in particular a radiation curing coating such as a radiation curing printing ink |
| WO2023138842A1 (en) * | 2022-01-19 | 2023-07-27 | Hubergroup Deutschland Gmbh | A rosin polymer to be used as inert component in a coating, in particular a radiation curing coating such as a radiation curing printing ink |
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| CN100415789C (en) | 2008-09-03 |
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