CN104356328B - Preparation method of soybean oil rosin combined chemical modified phenolic resin and modified phenolic resin - Google Patents
Preparation method of soybean oil rosin combined chemical modified phenolic resin and modified phenolic resin Download PDFInfo
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- CN104356328B CN104356328B CN201410586431.0A CN201410586431A CN104356328B CN 104356328 B CN104356328 B CN 104356328B CN 201410586431 A CN201410586431 A CN 201410586431A CN 104356328 B CN104356328 B CN 104356328B
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Abstract
The invention discloses a preparation method of soybean oil rosin combined chemical modified phenolic resin. The preparation method comprises the following steps: firstly, synthesizing epoxidized soybean oil, then, reacting the epoxidized soybean oil with methyl alcohol to generate soybean oil-based polyhydric alcohol and introducing a soybean oil molecular chain into the rosin modified phenolic resin by utilizing esterification reaction. The invention also discloses the soybean oil rosin combined chemical modified phenolic resin prepared by the method. The preparation method of the soybean oil rosin combined chemical modified phenolic resin and the modified phenolic resin have the advantages that the dissolving capacity of the soybean oil rosin combined chemical modified phenolic resin in soybean oil is excellent, soybean oil ink can be made without using any mineral oil, and the property of the soybean oil ink is basically similar to that of traditional similar ink, so that the soybean oil ink can completely replace the existing traditional ink; meanwhile, the soybean oil rosin combined chemical modified phenolic resin is environment-friendly, is free from pollution and has a wide market prospect.
Description
Technical field
The invention belongs to phenolic resins field, be specifically related to a kind of soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified
Preparation method and the phenol-formaldehyde resin modified be made up of the method.
Background technology
At tradition Printing ink producing with during using, VOC can volatilize in a large number (especially after ink printing, ink dry
The dry volatilization substantially completely relying on mineral oil), thus cause the most serious atmospheric pollution.Meanwhile, tradition ink production,
Printing and cleaning manufactures or during printing equipment, and the working environment of high concentration VOC can healthy to operator
(particularly nervous system) causes greatly infringement.Even low concentration VOC environment, Long Term Contact can make chapped skin coarse, also
Can penetrate into skin or blood vessel, and jeopardize blood cell and the hematopoietic function of people with blood, also can cause human body chronic poisoning.
Along with the deterioration rapidly of global ecological environment pollution problem, Global Oil resource exhaustion and oil price day by day in addition
Skyrocketing, the price from the mineral oil of the technical processs such as Petroleum refining reformation the most constantly rises, and the most effectively reduces ink
Middle VOC content has become various countries and has curbed environmental pollution the task of top priority of problem.Countries in the world formulate strict ring the most successively now
Protect decree regulation (as European Union in 2004 has issued and implemented " WEEE " and " ROHS " environmental protection act, calendar year 2001 Japan's issuing and implementation
" PRTR " environmental protection act), farthest to limit using and discharging of VOC, the most all kinds of leaflets are carried out very
Strict control, has become as the product that Chinese exports contains printed matter and (such as posts the toy of a large amount of label, electronic product
Deng) environmental protection barrier.
Constantly appearance and China of above decree are increasingly stricter to the requirement of environmental protection, are main to contracting extroversion economical
Chinese printing industry and ink manufacturing industry bring acid test and impact.Therefore, low VOC even Diamond Search how is manufactured
Environmental type ink become China's printing industry and ink industry problem anxious to be resolved.
Owing to the VOC emission of tradition ink is one of primary pollution source, therefore to exploitation one can substitute with mineral
Oil is as the environment-friendlyink ink kind of traditional ink of solvent composition, and countries in the world research staff has carried out a lot of research and probe,
Develop the environment-friendly ink product of a series of pollution-free or low VOC, such as water color ink, UV ink, alcohol-soluble printing ink, aqueous UV
Ink and soya-bean ink etc., success and strikingly development and application soya-bean ink (Soybean oil the most
Ink).
For the angle of recipe ingredient, soya-bean ink refers to the soybean oil replacing section nontoxic with green natural or whole
The environmental type ink of mineral oil, and the binder (resin system being dissolved by a solvent or having diluted；Resin can also be independent
Be referred to as link stuff), color stuffing and auxiliary agent the same in composition.Why soya-bean ink becomes world today's environmental protection
The main flow of type ink and future developing trend, reason is that it possesses the feature of environmental protection of excellence and printing.
Soya-bean ink has obtained extensively application in the developed country such as American-European-Japanese, but domestic soya-bean ink is the most at the early-stage,
Production technology is nearly at blank, to a great extent dependence on import.Though the domestic manufacturing enterprise having a few family to set foot in soya-bean ink,
But production capacity is less than normal, backward in technique, kind is the most complete.It addition, ink multinational corporations increases investment in China dynamics, because of it technically
It is in monopoly position, and there is the priority that introduction production type is supporting, make domestic pharmaceutical industry enterprise be in the ground restricted all the time
Position.Therefore exploitation has the offset printing soya-bean ink of China's independent intellectual property right, to breaking away from China's Printing Industry to foreign technology
Rely on, improve the international competitiveness of ink industry, promote China's ink industry and printing industry to energy-saving and emission-reduction and green manufacturing
Direction develop, be respectively provided with highly important meaning.
The main still rosin modified phenolic resin of current domestic offset litho printing ink binder resin, its printing performance is relatively
Good, but dissolubility is poor, needs to use more mineral oil, and the ink VOC content the most thus made is high, environmental pollution
Seriously.And the shortcoming that there is also the aberrations in property such as thermostability, resistance to water, alkali resistance after its film forming.Therefore, the green ring of exploitation
The fundamental way of guarantor's type soya-bean ink is the High Performance Phenolic Resins being developed to have excellent dissolution ability in soybean oil.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified, the party
Method is by introducing soybean oil on the strand of rosin modified phenolic resin, it is thus possible to effectively improve rosin modified phenolic resin
Solvability in soybean oil.
The present invention also aims to provide the preparation side utilizing above-mentioned soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified
The phenol-formaldehyde resin modified that method is made, this phenol-formaldehyde resin modified is good as link stuff solvability in soybean oil, and environmental protection is right
Environmental nonpollution.
First purpose in the present invention is achieved through the following technical solutions: a kind of soybean oil Colophonium associating chemistry
The preparation method of phenol-formaldehyde resin modified, comprises the following steps:
(1) soybean oil and solid super-strong acid are mixed, be warming up to 70～85 DEG C, add hydrogen peroxide, be incubated after addition
Reaction 6～8h, reacts complete dehydration and obtains epoxy soybean oil；
(2) methanol is added in the epoxy soybean oil prepared in step (1), be warming up to 90 ~ 110 DEG C, insulation reaction 3 ~ 5h,
Being down to room temperature and be filtered to remove solid phase, then washing is until system is neutrality repeatedly, finally dehydration obtains soybean oil base polyol；
(3) phenol, aldehyde and oxalic acid are added in reaction vessel, are warming up to 60～75 DEG C, after reaction 6～8h, stopped reaction, then
Dehydration obtains linear phenolic resin prepolymer；
(4) Colophonium joined in reaction vessel and be warming up to 120～130 DEG C, after Colophonium is completely melt, adding step
(3) the linear phenolic resin prepolymer in, then be warming up to 205～210 DEG C and insulation reaction 1～2h, be warming up to the most again 270～
280 DEG C and put into the soybean oil base polyol in step (2), other polyhydric alcohol and catalyst and continue insulation reaction 3～5h, stop
Only reaction, discharging, i.e. obtains soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified.
In the preparation method of above-mentioned soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified:
Step of the present invention (1) is utilize effective catalyst solid super-strong acid to react to prepare epoxy soybean oil, this stage
Becoming active epoxidizing agent without Mr., but directly use hydrogen peroxide that soybean oil is carried out epoxidation, course of reaction is simple, ring
Guarantor, efficient, low energy consumption.
Solid super-strong acid described in step (1) is preferably SO4 2-/ZrO2-TiO2、SO4 2-/ZrO2-Fe2O3-Cr2O3With
SO4 2-/ZrO2-Fe2O3-MnO2In one or more combination in any, these solid super-strong acids are preferably commercially available prod；
Described solid super-strong acid is preferably 0.015～0.035:1 with the mass ratio of soybean oil.
H in hydrogen peroxide described in step (1)2O2It is preferably 0.6～0.7:1 with the mass ratio of soybean oil.
Step of the present invention (2) utilizes the solid super-strong acid of residual in step (1) make catalyst, by epoxy soybean oil and
Methanol generation opening generates soybean oil base polyol.The commonly used strong acid of prior art is (such as concentrated hydrochloric acid, concentrated sulphuric acid
Deng) it is catalyst, in organic solvent system (such as acetone, butanone, DMF etc.), reaction generates soybean oil base polyol, existing
Synthetic technology later stage separating treatment difficulty, and pollute the most serious.
The present invention does not use any organic solvent, methanol and epoxy soybean oil to synthesize under the catalytic action of solid super-strong acid
Obtaining soybean oil base polyol, not only later stage separating treatment is simple, and does not has environmental pollution, also reduces simultaneously and generates into
This.
Methanol described in step (2) is preferably 1.8 ~ 2.5:1 with the mass ratio of epoxy soybean oil.
In step (2) effect of washing be super acids be will some water solublity in the acid that generates of reaction and soybean oil
Material remove.
Step of the present invention (3) is, under the catalytic action of oxalic acid, prepared by raw material phenol and aldehyde reaction linear phenolic resin pre-polymerization
Thing.
Phenol described in step (3) is preferably parater-butylphenol, in tert-octylphenol and dodecyl phenol
Kind or two or more combination in any；Described aldehyde is preferably formaldehyde and/or paraformaldehyde.
Described phenol and the mass ratio of aldehyde are preferably 1/3～2:1, and described oxalic acid and the mass ratio of phenol are preferably
0.01～0.25:1.
Step of the present invention (4) is first with Colophonium, phenolic resin carried out chemical modification, then draws during esterification
Enter soybean oil subchain.Utilize the conjugated double bond in Colophonium to occur D-A Diene-addition to react with phenolic aldehyde prepolymer, thus reach to increase
Big molecular resin amount, improves the purpose of resin application performance.On the one hand soybean oil base polyol and other polyhydric alcohol can reduce
The acid number of resin, improves the viscosity of resin, softening point and water-resistance, on the other hand can introduce soybean oil subchain, thus carry
High resin solubility property in soybean oil.
Colophonium described in step (4) is preferably 0.2～0.4:1 with the mass ratio of linear phenolic resin prepolymer.
Soybean oil base polyol described in step (4) is preferably 0.1 with the mass ratio of linear phenolic resin prepolymer
～0.3:1；The mass ratio of other described polyhydric alcohol and linear phenolic resin prepolymer is preferably 0.2～0.5:1, described
Catalyst is preferably 0.001～0.005:1 with the mass ratio of linear phenolic resin prepolymer.
Other described polyhydric alcohol is preferably tetramethylolmethane and/or glycerol；Described catalyst is preferably beryllium oxide, oxygen
Change one or more the combination in any in lithium, magnesium oxide, calcium oxide and zinc oxide.
Second object of the present invention is achieved through the following technical solutions: use above-mentioned soybean oil Colophonium to combine
The soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified that the preparation method of chemical modification phenolic resin is made.
Compared with prior art, present invention have the advantage that
(1) present invention is with natural reproducible resource soybean oil as starting material, first synthesizing epoxy soybean oil, then by it with low
Honest and clean methanol reaction generates soybean oil base polyol, finally joins as esterifying agent in the esterification process of rosin phenolic resin
With reaction, thus it is successfully introduced into soybean oil subchain；
(2) the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified not only molecular weight that prepared by the present invention is high, and acid number is low, color and luster
Pure, it is suitable as the link stuff of ink, and owing to employing substantial amounts of soybean oil base polyol, the soybean oil therefore made
In Colophonium associating chemistry phenol-formaldehyde resin modified, soybean oil content is high, and this phenol-formaldehyde resin modified presents highly dissoluble in soybean oil
Feature, need not use any volatile organic solvent when preparing ink, therefore meets the environment protection requirement of Diamond Search；
(3) soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified solvability in soybean oil that prepared by the present invention is excellent,
Any mineral oil can not be used i.e. to can be made into soya-bean ink, this soya-bean ink performance substantially close to traditional same type ink,
Existing tradition ink can be substituted completely, there is wide market prospect.
Detailed description of the invention
Embodiment 1
The preparation method of the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified that the present embodiment provides, comprises the following steps:
(1) by 1000 portions of soybean oils and 15 parts of solid super-strong acid SO4 2-/ZrO2-TiO2Mixing, is warming up to 70 DEG C, at the uniform velocity drips
Entering the hydrogen peroxide of 3000 part of 20% mass concentration, insulation reaction 6h after dropping, reacting the dehydration of complete evacuation, to obtain epoxy big
Oleum Glycines；
(2) 1800 parts of methanol are put in 1000 parts of epoxy soybean oils, be warming up to 100 DEG C, insulation reaction 3h, it is down to room temperature
Being filtered to remove solid phase, then washing is until system is neutrality repeatedly, the dehydration of last evacuation obtains soybean oil base polyol；
(3) tert-octylphenol, 3000 parts of formaldehyde and 10 parts of oxalic acid are added in reactor by 1000 parts, are warming up to 60
DEG C, after reaction 6h, stopped reaction, then vacuum dehydration i.e. obtains linear phenolic resin prepolymer；
(4) 200 parts of Colophonium put in reactor and be warming up to 120 DEG C, after Colophonium is completely melt, adding 1000 parts
Linear phenolic resin prepolymer, then it is warming up to 205 DEG C and insulation reaction 1h, it is warming up to 270 DEG C the most again and puts into 100 portions of Semen sojae atricolor
Based oil, 200 parts of tetramethylolmethanes and 1 part of catalyst Z nO also continue insulation reaction 3h, stopped reaction, discharging, i.e. obtain big
Oleum Glycines Colophonium associating chemistry phenol-formaldehyde resin modified product A.
Embodiment 2
The preparation method of the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified that the present embodiment provides, comprises the following steps:
(1) by 1000 portions of soybean oils and 35 parts of solid super-strong acid SO4 2-/ZrO2-TiO2Mixing, is warming up to 85 DEG C, at the uniform velocity drips
Enter the hydrogen peroxide of 3500 part of 20% mass concentration, insulation reaction 8h after dropping, react the dehydration of complete stratification and obtain epoxy
Soybean oil；
(2) 2500 parts of methanol are put in 1000 parts of epoxy soybean oils, be warming up to 100 DEG C, insulation reaction 5h, it is down to room temperature
Being filtered to remove solid phase, then washing is until system is neutrality repeatedly, the dehydration of last evacuation obtains soybean oil base polyol；
(3) tert-octylphenol, 1000 parts of formaldehyde and 250 parts of oxalic acid are added in reactor by 2000 parts, are warming up to 75
DEG C, after reaction 8h, stopped reaction, then vacuum dehydration i.e. obtains linear phenolic resin prepolymer；
(4) 400 parts of Colophonium put in reactor and be warming up to 130 DEG C, after Colophonium is completely melt, adding 1000 parts
Linear phenolic resin prepolymer, then it is warming up to 210 DEG C and insulation reaction 2h, it is warming up to 280 DEG C the most again and puts into 300 portions of Semen sojae atricolor
Based oil, 400 parts of glycerol and 5 parts of catalyst Z nO also continue insulation reaction 5h, stopped reaction, and discharging i.e. obtains Semen sojae atricolor
Oil rosin associating chemistry phenol-formaldehyde resin modified product B.
Embodiment 3
The preparation method of the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified that the present embodiment provides, comprises the following steps:
(1) by 1000 portions of soybean oils and 20 parts of mixed solid superacid (SO4 2-/ZrO2-TiO2And SO4 2-/ZrO2-Fe2O3-
MnO2Use with according to mass ratio 1:1) mixing, it is warming up to 75 DEG C, at the uniform velocity instills the hydrogen peroxide of 3200 part of 20% mass concentration, dropping
After insulation reaction 7h, react complete evacuation dehydration obtain epoxy soybean oil；
(2) 2000 parts of methanol are put in 1000 parts of epoxy soybean oils, be warming up to 100 DEG C, insulation reaction 4h, it is down to room temperature
Being filtered to remove solid phase, then washing is until system is neutrality repeatedly, the dehydration of last evacuation obtains soybean oil base polyol；
(3) by 1000 parts of mixed phenols (mixed according to mass ratio 1:1 with dodecyl phenol to tert-octylphenol), 1000 parts
Paraformaldehyde and 100 parts of oxalic acid are added in reactor, are warming up to 65 DEG C, after reaction 7h, and stopped reaction, then vacuum dehydration and get final product
To linear phenolic resin prepolymer；
(4) 300 parts of Colophonium put in reactor and be warming up to 125 DEG C, after Colophonium is completely melt, adding 1000 parts
Linear phenolic resin prepolymer, then it is warming up to 208 DEG C and insulation reaction 1.5h, it is warming up to 275 DEG C the most again and puts into 200 parts greatly
Soybean oil-based polyol, 300 parts of other polyhydric alcohol and 2 parts of mixed catalyst (Li2O with ZnO is mixed according to mass ratio 1:1) and continue
Insulation reaction 4h, stopped reaction, discharging, i.e. obtain soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified products C.
Embodiment 4
The preparation method of the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified that the present embodiment provides, comprises the following steps:
(1) by 1000 portions of soybean oils and 30 parts of mixed solid superacid (SO4 2-/ZrO2-TiO2、SO4 2-/ZrO2-Fe2O3-
Cr2O3And SO4 2-/ZrO2-Fe2O3-MnO2Use with according to mass ratio 1:2:1) mixing, it is warming up to 75 DEG C, at the uniform velocity instills 3400 parts
The hydrogen peroxide of 20% mass concentration, insulation reaction 7h after dropping, react the dehydration of complete evacuation and obtain epoxy soybean oil；
(2) 2200 parts of methanol are put in 1000 parts of epoxy soybean oils, be warming up to 100 DEG C, insulation reaction 4h, it is down to room temperature
Being filtered to remove solid phase, then washing is until system is neutrality repeatedly, the dehydration of last evacuation obtains soybean oil base polyol；
(3) by 1000 parts of mixed phenols (parater-butylphenol is mixed according to mass ratio 3:1 with dodecyl phenol), 1000 parts
Mixed aldehyde (formaldehyde is mixed according to mass ratio 2:1 with paraformaldehyde) and 200 parts of oxalic acid are added in reactor, are warming up to 65 DEG C,
After reaction 7h, stopped reaction, then vacuum dehydration i.e. obtains linear phenolic resin prepolymer；
(4) 350 parts of Colophonium put in reactor and be warming up to 125 DEG C, after Colophonium is completely melt, adding 1000 parts
Linear phenolic resin prepolymer, then it is warming up to 210 DEG C and insulation reaction 1h, it is warming up to 270 DEG C the most again and puts into 260 portions of Semen sojae atricolor
Based oil, 340 parts of polyols blends (tetramethylolmethane is mixed according to quality 3:1 with glycerol) and 4 parts of mixed catalysts
(Li2O, CaO are mixed according to mass ratio 1:1:2 with MgO) and continue insulation reaction 5h, stopped reaction, discharging, i.e. obtain soybean oil
Colophonium associating chemistry phenol-formaldehyde resin modified product D.
Soybean oil rosin modified phenolic resin A ~ D in embodiment 1-4 is the most mixed with soybean oil according to the mass ratio of 3:7
Closing, be sufficiently stirred for rear test system viscosity, degree of receiving, refer to sense of touch, set speed, test result is as shown in table 1；Add and account for greatly
The iron oxide yellow pigments of 15% mass fraction of Oleum Glycines rosin modified phenolic resin, is fully ground after being sufficiently stirred for again, finally glues
Degree, viscosity, set speed, color, glossiness, test result is as shown in table 2.
The soybean oil solution property test of table 1 soybean oil rosin modified phenolic resin
Table 2 ink performance is tested
From Tables 1 and 2, the soybean oil Colophonium prepared by the present invention combine chemistry phenol-formaldehyde resin modified at soybean oil
Middle solubility property is excellent, and receiving degree, set speed and the performances such as sense of touch that refer to meet application requirement；Combined by this soybean oil Colophonium
The soya-bean ink that chemical modification resin is prepared as link stuff meets ink application requirement at drying property and combination property, every
Substantially close to tradition ink, and without using any organic solvent, being used alone soybean oil is that solvent i.e. can be made into soybean oil
Ink, its VOC is zero, is real environment-friendlyink ink.Therefore, the soybean oil Colophonium associating chemistry modified phenolic prepared by the present invention
Resin has the strongest market competitiveness, and market prospect is fabulous, it is contemplated that the economic benefit of generation is huge.
The above-mentioned purpose with reference to embodiment is to describe the present invention, and is illustrative rather than limited
's.It will be understood by those skilled in the art that on the premise of without departing substantially from the scope of the present invention and general plotting, according to the side of the present invention
Method is made different modifications and variations and is apparent from, within should belonging to protection scope of the present invention.
Claims (4)
1. the preparation method of a soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified, it is characterised in that comprise the following steps:
(1) soybean oil and solid super-strong acid are mixed, be warming up to 70～85 DEG C, add hydrogen peroxide, insulation reaction 6 after addition
～8h, react complete dehydration and obtain epoxy soybean oil；
(2) methanol is added in the epoxy soybean oil prepared in step (1), be warming up to 90 ~ 110 DEG C, insulation reaction 3 ~ 5h, is down to
Room temperature is filtered to remove solid phase, then washing is until system is neutrality repeatedly, and finally dehydration obtains soybean oil base polyol；
(3) phenol, aldehyde and oxalic acid are added in reaction vessel, are warming up to 60～75 DEG C, after reaction 6～8h, stopped reaction, then be dehydrated
Obtain linear phenolic resin prepolymer；
(4) Colophonium joined in reaction vessel and be warming up to 120～130 DEG C, after Colophonium is completely melt, adding step (3)
In linear phenolic resin prepolymer, then be warming up to 205～210 DEG C and insulation reaction 1～2h, be warming up to 270～280 the most again
DEG C and put into the soybean oil base polyol in step (2), other polyhydric alcohol and catalyst and continue insulation reaction 3～5h, stop
Reaction, discharging, i.e. obtain soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified；
Solid super-strong acid described in step (1) is SO4 2-/ZrO2-TiO2、SO4 2-/ZrO2-Fe2O3-Cr2O3And SO4 2-/ZrO2-
Fe2O3-MnO2In one or more combination in any；Described solid super-strong acid with the mass ratio of soybean oil is
0.015～0.035:1；
H in hydrogen peroxide described in step (1)2O2It is 0.6～0.7:1 with the mass ratio of soybean oil；
Methanol described in step (2) is 1.8 ~ 2.5:1 with the mass ratio of epoxy soybean oil；
The mass ratio of the phenol described in step (3) and aldehyde is (1/3～2): 1, and described oxalic acid and the mass ratio of phenol are
0.01～0.25:1；
Colophonium described in step (4) is 0.2～0.4:1 with the mass ratio of linear phenolic resin prepolymer；
Soybean oil base polyol described in step (4) is 0.1～0.3:1 with the mass ratio of linear phenolic resin prepolymer；
Other described polyhydric alcohol is 0.2～0.5:1 with the mass ratio of linear phenolic resin prepolymer, and described catalyst is with linear
The mass ratio of phenolic resin prepolymer is 0.001～0.005:1.
The preparation method of soybean oil Colophonium the most according to claim 1 associating chemistry phenol-formaldehyde resin modified, it is characterised in that:
Phenol described in step (3) is parater-butylphenol, to one or more in tert-octylphenol and dodecyl phenol
Combination in any；Described aldehyde is formaldehyde and/or paraformaldehyde.
The preparation method of soybean oil Colophonium the most according to claim 1 associating chemistry phenol-formaldehyde resin modified, it is characterised in that:
Other described polyhydric alcohol is tetramethylolmethane and/or glycerol；Described catalyst is beryllium oxide, lithium oxide, magnesium oxide, oxidation
One or more combination in any in calcium and zinc oxide.
4. the preparation method using the soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified described in any one of claim 1-3 is made
Soybean oil Colophonium associating chemistry phenol-formaldehyde resin modified.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
| CN102911330A (en) * | 2012-10-16 | 2013-02-06 | 山西省应用化学研究所 | Vegetable oil modified rosin phenolic resin and preparation method thereof |
| CN103657696A (en) * | 2013-12-12 | 2014-03-26 | 中科院广州能源所盱眙凹土研发中心 | Preparation method of attapulgite-based solid acid catalyst for vegetable fat epoxidation |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
| CN102911330A (en) * | 2012-10-16 | 2013-02-06 | 山西省应用化学研究所 | Vegetable oil modified rosin phenolic resin and preparation method thereof |
| CN103657696A (en) * | 2013-12-12 | 2014-03-26 | 中科院广州能源所盱眙凹土研发中心 | Preparation method of attapulgite-based solid acid catalyst for vegetable fat epoxidation |
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Effective date of registration: 20180704 Address after: 528400 Zhong Heng Industrial Avenue, Heng Lan town, Zhongshan, Guangdong Patentee after: Zhongshan Chant Paint Co., Ltd. Address before: No. 82, middle and horizontal Avenue in Guangdong, Zhongshan, Guangdong Patentee before: Zhongshan Kingho Chemical Co., Ltd. |