CN103540265A - Preparation method of liquid rosin resin - Google Patents
Preparation method of liquid rosin resin Download PDFInfo
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- CN103540265A CN103540265A CN201310483746.8A CN201310483746A CN103540265A CN 103540265 A CN103540265 A CN 103540265A CN 201310483746 A CN201310483746 A CN 201310483746A CN 103540265 A CN103540265 A CN 103540265A
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Abstract
The invention discloses a preparation method of liquid rosin resin. The preparation method comprises the following steps of (1), fusing solid rosin under the protection of inert gas, and reacting rosin with monobasic acid or binary acid under the action of a catalyst and the protection of antioxidant at 150-220 DEG C for 3-5 hours; (2), dropping liquid polyhydric alcohol, and reacting at 220-285 DEG C for 8-12 hours; and (3), decreasing the temperature and discharging after vacuumizing for 1-2 hours to obtain the liquid rosin resin. The liquid rosin resin prepared by the preparation method disclosed by the invention has the advantages of being low in glass state temperature and good in low-temperature fluidity and ageing resistance.
Description
[technical field]
The present invention relates to a kind of preparation method of liquid rosin resin.
[background technology]
In order to obtain good low-temperature fluidity, reduce low temperature brittleness, often take chemical modification that rosin is made to liquid rosin fat and be applied in the products such as sizing agent, especially under the cold and heat temperature difference and the huge environment for use of the region temperature difference, there is good low temperature flowability and lower low Tg liquid rosin resin just has stronger practical value.
[summary of the invention]
The preparation method who the object of this invention is to provide a kind of low Tg, liquid resin that low temperature flowability is good.
In order to achieve the above object, preparation method that the present invention adopts comprises step:
1. under protection of inert gas, molten solids rosin, rosin reacts with monoprotic acid or diprotic acid under catalyst action He under antioxidant protection, at 150-220 ℃ of reaction 3-5 hour.
2. drip liquid polyol, at 220-285 ℃ of reaction 8-12 hour.
3. cooling discharge after vacuumizing 1-2 hour, obtains liquid rosin resin.
Described rosin is gum resin or starex.
Described monoprotic acid or diprotic acid are one or more in vinylformic acid, fumaric acid, oleic acid, MALEIC ANHYDRIDE, and the quality of described monoprotic acid or diprotic acid is the 3%-25% of raw material rosin weight.The consumption of acid used is very large to the performance impact of product, consumption very little, the point being grafted to when synthetic on rosin molecule is insufficient, the DeGrain of modification, when consumption is too much, the excessive acid meeting polyol reaction in directly reacting with step 2, becomes unnecessary side reaction, directly affects the result of use of derived product.Described monoprotic acid or diprotic acid are preferably vinylformic acid or oleic acid, can improve better flexibility and the flowing property of rosin molecule.
Described polyvalent alcohol is one or more in glycerine, isooctyl alcohol, polyether glycol 220, polyoxyethylene glycol, Diethylene Glycol, triethylene glycol; Preferably, described polyvalent alcohol is Diethylene Glycol, one or more of triethylene glycol or isooctyl alcohol, and the quality of described polyvalent alcohol is the 5%-35% of raw material rosin weight;
Described catalyzer is technical grade zinc oxide or lithium hydroxide, and the quality that described catalyzer can reduce pyroreaction time 3 hours described catalyzer is the 0.05%-0.1% of described rosin total mass, and more preferably, described catalyzer is lithium hydroxide.
Described antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, one or more in 4,4-thiobis (the 6-tertiary butyl-3-methylphenol), described oxidation inhibitor can lower a look 2-3 rank of resin finished product, and the quality of described oxidation inhibitor is 0.15% of described raw material rosin weight.
As the preferred implementation of liquid resin of the present invention, affiliated liquid rosin resin body chemical composition is acrylic acid modified rosin glycol ester.
The method of the invention adopts chemic modified method to change rosin molecular structure, two keys and carboxyl in abundant modified rosin molecule, and acid number is 45 to the maximum, and second-order transition temperature is minimum reaches-30 ℃, viscosity is less than 140PA.S(50 ℃).It is good that resin after modification has ageing-resistant performance, low Tg, the feature that low-temperature fluidity is good, Realization of Product commercial scale production and put remarkable in economical benefits on market.
[embodiment]
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
A resin, adopts following methods preparation;
By 300 grams of starex, its pulverizing is packed in reaction vessel, add 0.3 gram of catalyzer lithium hydroxide and three (2 simultaneously, 4-di-tert-butyl-phenyl) phosphorous acid ester is 0.45 gram, inflated with nitrogen heats up, and slowly drips 20 grams, vinylformic acid when temperature rises to 150 ℃, drips off rear insulation 3 hours; Drip 90 grams of triethylene glycols, 250 ℃ of insulations, after 8 hours, vacuumize 1.5 hours, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of this enforcement gained liquid rosin resin is 6 grades (adding nanofarad), appearance transparent, and acid number is 23.5 mgKOH/g, second-order transition temperature is minimum reaches-25 ℃, viscosity 60.5PA.S(50 ℃).
Embodiment 2
A resin, adopts following methods preparation;
By 300 grams of gum resin, its pulverizing is packed in reaction vessel, add 0.3 gram of catalyzer lithium hydroxide and three (2 simultaneously, 4-di-tert-butyl-phenyl) phosphorous acid ester is 0.45 gram, inflated with nitrogen heats up, and slowly drips 20 grams, vinylformic acid when temperature rises to 150 ℃, drips off rear insulation 3 hours; Drip 80 grams of Diethylene Glycols, 220 degree insulations, after 10 hours, vacuumize 1 hour, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of liquid resin of the present invention is 5 grades (adding nanofarad), appearance transparent, and acid number is 22mgKOH/g, second-order transition temperature is minimum reaches-20 ℃, viscosity 70.5PA.S(50 ℃).
Embodiment 3
A resin, adopts following methods preparation;
By 300 grams of exquisite rosin, its pulverizing is packed in reaction vessel, add 0.3 gram of catalyzer lithium hydroxide and three (2 simultaneously, 4-di-tert-butyl-phenyl) phosphorous acid ester is 0.45 gram, inflated with nitrogen heats up, and slowly drips 20 grams, vinylformic acid when temperature rises to 150 ℃, drips off rear insulation 3 hours; Second step reaction drips 80 grams of Diethylene Glycols, and 230 degree insulations, after 9.5 hours, vacuumize 2 hours, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of liquid resin of the present invention is 4 grades (adding nanofarad), appearance transparent, and acid number is 23.5mgKOH/g, second-order transition temperature is minimum reaches-20.5 ℃, viscosity 71.2PA.S(50 ℃).
Embodiment 4
A resin, adopts following methods preparation;
By 300 grams of gum resin, its pulverizing is packed in reaction vessel, add 0.3 gram, catalyst oxidation zinc and 4 simultaneously, 0.45 gram of 4-thiobis (the 6-tertiary butyl-3-methylphenol), inflated with nitrogen heats up, and slowly drips 33 grams, vinylformic acid when temperature rises to 200 ℃, drips off rear insulation 3 hours; Second step reaction drips (330) 45 grams of polyether glycols, and 270 ℃ of insulations, after 8 hours, vacuumize 2 hours, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin polyether polyol esters.
The color of liquid resin of the present invention is 6 grades (adding nanofarad), appearance transparent, and acid number is 45mgKOH/g, second-order transition temperature is minimum reaches-15 ℃, viscosity 70.2PA.S(50 ℃).
Embodiment 5
A resin, adopts following methods preparation;
By 300 grams of gum resin, its pulverizing is packed in reaction vessel, add 0.3 gram, catalyst oxidation zinc and 4 simultaneously, 0.45 gram of 4-thiobis (the 6-tertiary butyl-3-methylphenol), inflated with nitrogen heats up, and slowly drips 20 grams, vinylformic acid when temperature rises to 150 ℃, drips off rear insulation 5 hours; Drip 55 grams of Diethylene Glycols, 220 insulations 12 hours, vacuumize 1.5 hours, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of liquid resin of the present invention is 5 grades (adding nanofarad), appearance transparent, and acid number is 45 mgKOH/g, second-order transition temperature is minimum reaches-25.8 ℃, viscosity 20PA.S(40 ℃).
Embodiment 6
A resin, adopts following methods preparation;
By 300 grams of gum resin, its pulverizing is packed in reaction vessel, add 0.3 gram, catalyst oxidation zinc and 4 simultaneously, 0.45 gram of 4-thiobis (the 6-tertiary butyl-3-methylphenol), inflated with nitrogen heats up, when temperature rises to 150 ℃, slowly drip 15 grams, vinylformic acid, drip off latter 5 hours; Second step reaction drips 65 grams of Diethylene Glycols, and 270 ℃ of insulations, after 8 hours, vacuumize 2 hours, cooling discharge, and obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of liquid rosin resin of the present invention is 5 grades (adding nanofarad), appearance transparent, and acid number is 25.2 mgKOH/g, second-order transition temperature is minimum reaches-15 ℃, viscosity 102.5PA.S(50 ℃).
Embodiment 7
A resin, adopts following methods preparation;
By 300 grams of gum resin, its pulverizing is packed in reaction vessel, add 0.3 gram, catalyst oxidation zinc and 4 simultaneously, 0.45 gram of 4-thiobis (the 6-tertiary butyl-3-methylphenol), inflated with nitrogen heats up, and slowly drips 60 grams, vinylformic acid when temperature rises to 210 ℃, drips off rear insulation 3 hours; Second step reaction drips 70 grams of triethylene glycols, and 280 ℃ of insulations, after 8 hours, vacuumize 2 hours, cooling discharge.Obtaining main body composition is the liquid rosin resin of acrylic acid modified rosin glycol ester.
The color of liquid rosin resin of the present invention is 6 grades (adding nanofarad), appearance transparent, and acid number is 33.8 mgKOH/g, second-order transition temperature is minimum reaches-18 ℃, viscosity 82.5PA.S(50 ℃).
On the present invention is described in detail, the above, be only the present invention's preferred embodiment, do not limit the scope of the present invention, allly according to the application's scope, does impartial change and modify, and all should still belong in covering scope of the present invention.
Claims (8)
1. a preparation method for liquid rosin resin, comprises step:
(1) under protection of inert gas, molten solids rosin, rosin reacts with monoprotic acid or diprotic acid under catalyst action He under antioxidant protection, at 150-220 ℃ of reaction 3-5 hour;
(2) drip liquid polyol, at 220-285 ℃ of reaction 8-12 hour;
(3) vacuumize 1-2 hour after cooling discharge, obtain liquid rosin resin.
2. the preparation method of liquid rosin resin as claimed in claim 1, is characterized in that, described rosin is gum resin or starex.
3. the preparation method of liquid rosin resin as claimed in claim 1, is characterized in that, described monoprotic acid or diprotic acid are one or more in vinylformic acid, fumaric acid, oleic acid, MALEIC ANHYDRIDE.
4. the preparation method of liquid rosin resin as claimed in claim 1, is characterized in that, described polyvalent alcohol is one or more in glycerine, isooctyl alcohol, polyether glycol 220, polyether glycol 330, polyoxyethylene glycol, Diethylene Glycol, triethylene glycol.
5. the preparation method of liquid rosin resin as claimed in claim 1, is characterized in that, described catalyzer is technical grade zinc oxide or lithium hydroxide, and the quality of described catalyzer is the 0.05%-0.1% of raw material rosin weight.
6. the preparation method of liquid rosin resin as claimed in claim 1, it is characterized in that, described antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 4, one or more in 4-thiobis (the 6-tertiary butyl-3-methylphenol), the quality of described oxidation inhibitor is 0.15% of described raw material rosin weight.
7. the preparation method of the liquid rosin resin as described in claim 1 or 3, is characterized in that, the quality of described monoprotic acid or diprotic acid is the 3%-25% of raw material rosin weight.
8. the preparation method of the liquid rosin resin as described in claim 1 or 4, is characterized in that, the quality of described polyvalent alcohol is the 5%-35% of raw material rosin weight.
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| CN201310483746.8A CN103540265A (en) | 2013-10-16 | 2013-10-16 | Preparation method of liquid rosin resin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087178A (en) * | 2014-07-29 | 2014-10-08 | 广西众昌树脂有限公司 | Preparation method for crylic acid modified rosin glyceride |
| CN105623521A (en) * | 2016-03-21 | 2016-06-01 | 南京林业大学 | Method of rosin liquid dry distillation color subtraction |
| CN105838257A (en) * | 2016-04-15 | 2016-08-10 | 梧州市飞卓林产品实业有限公司 | Production method of alcohol-soluble rosin resin |
| CN107109092A (en) * | 2015-01-29 | 2017-08-29 | 哈利玛化成株式会社 | Hectographic printing black liquid resin |
| CN107254023A (en) * | 2017-06-26 | 2017-10-17 | 四会市邦得利化工有限公司 | Preparation method and application of graft modified tackifying resin |
| CN107619642A (en) * | 2017-09-25 | 2018-01-23 | 广西众昌树脂有限公司 | The preparation method of liquid rosin resin |
| CN113292927A (en) * | 2021-05-31 | 2021-08-24 | 江西金安林产实业有限公司 | Rosin resin for moisture-curing reactive hot melt adhesive and preparation method thereof |
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| CN102993977A (en) * | 2012-12-21 | 2013-03-27 | 广西梧州日成林产化工股份有限公司 | Preparation method of triethylene glycol hydrogenated rosinate |
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| JP2008266597A (en) * | 2007-03-22 | 2008-11-06 | Arakawa Chem Ind Co Ltd | Polymeric rosin, hydrogenated polymeric rosin and production method of these rosins, as well as flux and solder paste using these rosins |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087178A (en) * | 2014-07-29 | 2014-10-08 | 广西众昌树脂有限公司 | Preparation method for crylic acid modified rosin glyceride |
| CN107109092A (en) * | 2015-01-29 | 2017-08-29 | 哈利玛化成株式会社 | Hectographic printing black liquid resin |
| CN107109092B (en) * | 2015-01-29 | 2020-09-18 | 哈利玛化成株式会社 | Resin for offset printing ink |
| CN105623521A (en) * | 2016-03-21 | 2016-06-01 | 南京林业大学 | Method of rosin liquid dry distillation color subtraction |
| CN105623521B (en) * | 2016-03-21 | 2018-05-22 | 南京林业大学 | A kind of rosin liquid dry distillation color subtractive processes |
| CN105838257A (en) * | 2016-04-15 | 2016-08-10 | 梧州市飞卓林产品实业有限公司 | Production method of alcohol-soluble rosin resin |
| CN107254023A (en) * | 2017-06-26 | 2017-10-17 | 四会市邦得利化工有限公司 | Preparation method and application of graft modified tackifying resin |
| CN107254023B (en) * | 2017-06-26 | 2018-06-29 | 四会市邦得利化工有限公司 | Preparation method and application of graft modified tackifying resin |
| CN107619642A (en) * | 2017-09-25 | 2018-01-23 | 广西众昌树脂有限公司 | The preparation method of liquid rosin resin |
| CN113292927A (en) * | 2021-05-31 | 2021-08-24 | 江西金安林产实业有限公司 | Rosin resin for moisture-curing reactive hot melt adhesive and preparation method thereof |
| CN113292927B (en) * | 2021-05-31 | 2022-08-30 | 江西金安林产实业有限公司 | Rosin resin for moisture-curing reactive hot melt adhesive and preparation method thereof |
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Application publication date: 20140129 |