CN1067250A - The synthetic method of elaeomargaric acid series resorcinol formaldehyde resin - Google Patents
The synthetic method of elaeomargaric acid series resorcinol formaldehyde resin Download PDFInfo
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- CN1067250A CN1067250A CN 91103376 CN91103376A CN1067250A CN 1067250 A CN1067250 A CN 1067250A CN 91103376 CN91103376 CN 91103376 CN 91103376 A CN91103376 A CN 91103376A CN 1067250 A CN1067250 A CN 1067250A
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- acid
- resorcinol
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- eleostearate
- formaldehyde resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 111
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims abstract description 64
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims abstract description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 eleostearic acid acid amides Chemical class 0.000 claims abstract description 16
- 239000002383 tung oil Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 229960001755 resorcinol Drugs 0.000 claims description 60
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 150000004702 methyl esters Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 2
- 238000007098 aminolysis reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 229920003987 resole Polymers 0.000 abstract description 5
- 239000005011 phenolic resin Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000004304 visual acuity Effects 0.000 abstract description 3
- 238000012644 addition polymerization Methods 0.000 abstract 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 5
- 240000002834 Paulownia tomentosa Species 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- YDVRNIJXDWVHDB-UHFFFAOYSA-N 1,4-dioxane;2-ethoxyethanol Chemical compound CCOCCO.C1COCCO1 YDVRNIJXDWVHDB-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KOJYENXGDXRGDK-ZUGARUELSA-N 9(Z),11(E),13(E)-Octadecatrienoic Acid methyl ester Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(=O)OC KOJYENXGDXRGDK-ZUGARUELSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The synthetic method of elaeomargaric acid series resorcinol formaldehyde resin.With eleostearic acid or eleostearate earlier and the Resorcinol addition carry out polycondensation with formaldehyde again, perhaps first the and formaldehyde condensation of Resorcinol carries out addition polymerization with eleostearic acid or eleostearate again, the polymerisate of eleostearate carries out aminolysis again.Synthesized the resorcinol formaldehyde resin of eleostearic acid, eleostearate, eleostearic acid acid amides by this two kinds of similar methods, its softening temperature is at 60-110 ℃.Except that the purposes with previous tung oil phenol resin, these resol can be formed the photosensitive resin that a class has good characteristics such as high sensitivity, high resolving power, dilute alkaline developing together with photocrosslinking agents such as double azido compounds.
Description
The invention belongs to the synthetic method of eleostearic acid system (eleostearic acid, eleostearate, eleostearic acid acid amides) resorcinol formaldehyde resin.
FDAC changes into industrial and once invented and pyrocatechol is imported the synthetic technology of tung oil (JP60-228580A JP61-21122A), has broken through tung oil only to only importing the situation of monohydric phenol modification in phenolic resin modified or the tung oil.But the shortcoming of this technology is addition reaction must carry out under a large amount of excessive conditions of phenol, and low, the easy gelling of importing rate.Products therefrom can not be used normal temperature, quick photocuring, thereby can not satisfy the requirement of imaging or Micrometer-Nanometer Processing Technology.1988, we successfully imported Resorcinol tung oil (CN88101351), and had obtained the photosensitive resin of excellent property thus.But still there is the lower shortcoming of softening temperature in tung oil-resorcinol resin.
The objective of the invention is to tung oil and Resorcinol is main raw material, manages a synthetic class elaeomargaric acid series resorcinol resol, and its softening temperature is significantly increased than tung oil-Resorcinol, and film performance also improves.Except that the purposes that has the previous tung oil phenol resin concurrently, make this resinoid keep the characteristic that tung oil-Resorcinol and azide and thing carry out the light cross-linking reaction, to obtain the photosensitive resin that a class has good characteristics such as high sensitivity, high resolving power, dilute alkaline developing.
The present invention is realized by two kinds of similar methods.
First method is: with eleostearic acid or eleostearate or the two mixture and Resorcinol according to 1: the mol ratio of 1-5, the acid catalyst that adds reactant weight 0.01-5%, logical nitrogen, have or organic solvent-free in the presence of, 60-140 ℃ of reaction 1-5 hour, generate the Resorcinol affixture shown in [1]:
R in the formula
1=H, CH
3, CH
2CH
3, CH(CH
3)
2Deng, X can be one of structure shown in (A), (B), (C):
Wherein (A), (B) are major ingredient.Is 1 with the Resorcinol affixture of above-mentioned eleostearic acid or eleostearate or the two mixture and formalin according to wherein Resorcinol and formaldehyde: the mol ratio of 0.25-0.75, the acid catalyst that adds reactant weight 0.01-5% obtains the resorcinol formaldehyde resin of eleostearic acid or eleostearate or the two miscellany in 60-140 ℃ of reaction 2-6 hour.With eleostearate resorcinol formaldehyde resin and monoamine according to 1: the mol ratio of 0.5-5, in the presence of a small amount of organic solvent, in 140-170 ℃ of reaction 1-4 hour, obtain the resorcinol formaldehyde resin of eleostearic acid acid amides resorcinol formaldehyde resin or eleostearic acid acid amides and eleostearate miscellany.The composition of these resol can be expressed as:
R is that Resorcinol, T are eleostearic acid or eleostearate or eleostearic acid acid amides in the formula, n=0-300.
The optimum condition of present method is: eleostearic acid or eleostearic acid fat or the two miscellany and Resorcinol are according to 1: the molar ratio reaction of 1.5-2.5, selecting the phosphoric acid of reactant gross weight 0.5-2% or the tosic acid of trichoroacetic acid(TCA) or oxalic acid or 0.2-1% for use is catalyzer, solubilizing agent not, logical nitrogen was 100-130 ℃ of reaction 2-4 hour.
Resorcinol affixture that more than obtains and formalin are that to select the oxalic acid of 0.5-2% or the tosic acid of phosphoric acid or trichoroacetic acid(TCA) or 0.2-1% for use be catalyzer for 1: 0.5 mol ratio according to wherein Resorcinol and formaldehyde, add reactant weight 1-3 organic solvent doubly, earlier 60-100 ℃ of back flow reaction 1 hour, boil off the water in the system more gradually and improve temperature of reaction simultaneously, 100-120 ℃ of reaction 2-4 hour.
With eleostearic acid methyl esters resorcinol formaldehyde resin and thanomin or diethanolamine according to 1: the 1-3 mol ratio is carried out aminolysis reaction.
Second method of the present invention is: with eleostearic acid or eleostearate or the two mixture and resorcinol formaldehyde oligopolymer according to 1: the mol ratio of 0.25-2, the acid catalyst that adds the 0.01-5% of reactant weight, have or organic solvent-free in the presence of, 100-160 ℃ of reaction 2-6 hour, obtain the resorcinol formaldehyde resin of eleostearic acid or eleostearate or the two mixture.With the above eleostearate resorcinol formaldehyde resin that obtains and monoamine according to 1: the mol ratio of 0.5-5, in the presence of a small amount of organic solvent, 140-160 ℃ of reaction 1-4 hour, obtain the resorcinol formaldehyde resin of eleostearic acid acid amides resorcinol formaldehyde resin or eleostearic acid acid amides and eleostearate miscellany.The composition of these phenolic resins can be expressed as:
R is that Resorcinol, T are eleostearic acid or eleostearate or eleostearic acid acid amides in the formula, R-(-CH
2-R)
mBe resorcinol formaldehyde oligopolymer, m=1-3, n=0-100.
The optimum condition of present method is: with eleostearic acid or eleostearate or the two mixture and two Resorcinol formals according to 1: the mol ratio of 0.5-1.5, with the tosic acid of reactant gross weight 0.2-1% or phosphoric acid or the trichoroacetic acid(TCA) of 0.5-2% is that catalyzer is in the presence of the organic solvent of 30-50%, 120-150 ℃ of reaction 2-4 hour.With eleostearic acid methyl esters resorcinol formaldehyde resin and thanomin or diethanolamine according to 1: the mol ratio of 1-3 is carried out aminolysis.
More than these two kinds of similar methods all be to utilize addition reaction and the condensation reaction of Resorcinol and formaldehyde of Resorcinol on the eleostearic acid conjugated double bond to realize the synthetic of elaeomargaric acid series resorcinol formaldehyde resin.Its difference only is that the former carries out condensation reaction with formaldehyde again at advanced person's addition reaction of dihydroxy-benzene in the ranks, and the latter is that addition reaction is carried out in the condensation reaction of advanced dihydroxy-benzene in the ranks and formaldehyde again.The structure of the product of two kinds of methods is consistent under optimum condition.The latter relatively helps the importing rate of Resorcinol in the raising system.
The used tung oil of the present invention is the high iodine number tung oil that produces all over China.Contain in the eleostearic acid that makes by tung oil saponification, acid out a small amount of not with the lipid acid of resorcin reaction.Eleostearate can be obtained by eleostearic acid and alcohol (methyl alcohol, ethanol, Virahol etc.) direct esterification, makes catalyzer with the vitriol oil or tosic acid etc.Perhaps by eleostearic acid and epoxy chloropropane 100-140 ℃ of reaction, the N with 1%, the N-dimethyl benzylamine is made catalyzer.
Experiment shows that eleostearic acid or eleostearate or the two mixture and Resorcinol are according to 1: the mol ratio of 1-5; with the various acid as catalyst of reactant weight 0.01-5% have or organic solvent-free in the presence of when solvent-free (logical nitrogen protection); 60-140 ℃ of reaction, can both obtain the Resorcinol affixture.Improve the molecular weight of target product, softening temperature and buck dissolubility, the necessary importing rate that improves Resorcinol.Since contain approximately in the rough eleostearic acid 20% not with the lipid acid of resorcin reaction, under the excessive situation of Resorcinol, its importing rate is generally 1.2-1.4, therefore eleostearic acid or eleostearic acid fat or the two mixture and Resorcinol addition reaction preferred molar ratio are 1: 1.5-2.5, improve the ratio of Resorcinol again, only cause wave useless and bring difficulty to separation and purification.This reaction can be adopted Friedel-crafts reaction catalyzer such as acid catalysts such as tosic acid, trichoroacetic acid(TCA), phosphoric acid, oxalic acid and aluminum chloride, iron trichloride, zinc dichloride.But as adopting above Friedel-crafts reaction catalyzer, must conscientious separation and purification as sensitive materials.Above-mentioned various acid catalyst can both obtain catalytic effect preferably.Catalytic amount is few, and then speed of response is slower, and consumption is many may to be caused side reaction and cause waste.Its preferable amount is the tosic acid of reactant weight 0.2-1% or phosphoric acid or trichoroacetic acid(TCA) or the oxalic acid of 0.5-2%, and solubilizing agent does not lead to nitrogen protection 100-130 ℃ of reaction.When Resorcinol affixture and formalin carried out polycondensation, experiment showed that the mol ratio of Resorcinol and formaldehyde is 1: can both obtain polycondensation product during 0.25-0.75, but its optimum proportion is: 1: 0.5.When the amount of formaldehyde is higher than this ratio, particularly be higher than at 1: 0.75 o'clock, cause gelling easily.And the amount of formaldehyde is lower than at 1: 0.5 o'clock, and the content of its oligopolymer also increases gradually, is unfavorable for improving molecular weight and softening temperature.This catalysts and consumption can be the tosic acid of 0.2-1% or phosphoric acid or trichoroacetic acid(TCA) or the oxalic acid of 0.5-2%.Gelling takes place in catalytic amount too Da Yi, and then speed of response is slower very little for amount.Solvent can be selected the good organic solvent of solvability for use, and as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetic ester etc., consumption is 1-3 a times of reactant weight.Because contain portion water in the system, organic solvent amount solubility property very little is bad, quantity of solvent too greatly then speed of response is too slow.This reaction is back flow reaction 1 hour between 60-100 ℃ earlier, and formaldehyde is fully reacted, and improves temperature then and boils off water in the system, carries out finishing in polycondensation 2-4 hour between 100-120 ℃.
Experiment shows that eleostearic acid or eleostearate or the two miscellany and resorcinol formaldehyde oligopolymer are according to 1: the mol ratio of 0.25-2.5 under the acid catalysis of 0.01-5%, can both obtain polyaddition products 100-160 ℃ of reaction.In the resorcinol formaldehyde oligopolymer with the easiest preparation of two Resorcinol formal and Industrial products are arranged.Preferred eleostearic acid of the present invention or eleostearate or the two mixture and two Resorcinol formal carry out polyaddition reaction, and its reaction mol ratio is 1: 0.5-1.5.When this ratio is lower than 1: 0.5, two Resorcinol formals energy quantitative reactions, but be unfavorable for improving molecular weight and softening temperature, when this ratio was higher than 1: 1.5, the importing rate was 1.0-1.2, caused waste and brought difficulty to separation.This catalyst for reaction is similar with aforementioned Resorcinol addition reaction, but because the reactive behavior of two Resorcinol formals is lower than Resorcinol, can select the stronger tosic acid of catalytic capability for use, consumption is the 0.2-1% of reactant weight, also can select for use the phosphoric acid of 0.5-2% or trichoroacetic acid(TCA) to make catalyzer.Then speed of response is slower very little for catalyst levels, and consumption too greatly then may cause crosslinking reaction to take place.Reaction can be solvent-free; carry out under the logical nitrogen protection; but because the reaction product softening temperature is higher, preferably select for use solubility property well to have the ethylene glycol monoalkyl ether of higher or ethylene glycol monoalkyl ether acetic ester etc. to make solvent again, consumption is the 30-50% of reactant weight.Then speed of response is too slow and be unfavorable for improving temperature too much for amount.Being reflected at 120-150 ℃ carries out can finishing in 2-5 hour.The too low then speed of response of temperature is very slow, has side reaction even causes gelling as temperature is too high.
The eleostearate resorcinol formaldehyde resin that is obtained by above two kinds of similar methods all can carry out aminolysis reaction.Select for use eleostearic acid methyl esters resorcinol formaldehyde resin to carry out aminolysis, react the easiest carrying out.Because this reaction must just can be carried out under greater than 140 ℃ of temperature, amine can be selected high boiling point monoamines such as thanomin, diethanolamine for use.If with lower boiling monoamines such as diethylamine, then reaction must be carried out adding to depress.This reaction can directly be carried out after polycondensation or polyaddition reaction are finished, but need boil off most of solvent in the system so that its temperature of reaction reaches more than 140 ℃.When the mol ratio of eleostearate in the reactant and amine was lower than 1: 1, aminolysis was incomplete, was higher than at 1: 3 o'clock, a large amount of excessive the causing waste and necessary separation of amine.Therefore this reaction optimum condition be eleostearic acid methyl esters resorcinol formaldehyde resin and thanomin or diethanolamine according to 1: the mol ratio of 1-3 was reacted 2-3 hour at 140-160 ℃.
The present invention at the Friedel-crafts reaction that can successfully take place under the acid catalysis on hydrogen transference addition or the phenyl ring, has synthesized the resorcinol formaldehyde resin of a series of eleostearic acid, eleostearate, eleostearic acid acid amides from three conjugated double bonds of eleostearic acid and Resorcinol or resorcinol formaldehyde oligopolymer.The softening temperature of these resol is compared with tung oil-Resorcinol 60-110 ℃ of scope, and its softening temperature improves more than 50 ℃.Simultaneously, because the raising of molecular weight, its film performance also improves.Because activation point in basic adjacency pair position in residual a large amount of unreacted pair of keys and the Resorcinol in these resins, what they had kept tung oil-Resorcinol carries out the characteristic of photo-crosslinking with triazo-compound and polydentate compound.A large amount of phenolic group also makes it have good buck dissolubility.Therefore, the photosensitive resin that is made of these resol and double azido compound has high sensitivity (minimum curing light quantity is 15mj/cm
2About), good characteristic such as high resolving power (can obtain the etching wire spoke clearly of 3u), dilute alkaline developing.These photosensitive resins large-scale integrated circuit with photoresist, use in printed circuit board dry film photoresist, Printing industry can extensively be utilized with ps version sensitizer, wire printing plate-making photoresists and aspects such as silk-screen seal material and photo-hardening coating.
Introduce synthesis example of the present invention below.
[synthesis example 1-synthesis example 4]
The proportioning raw materials that provides according to table 1.At first in the four-hole reaction flask that agitator, thermometer and logical nitrogen pipe are housed, add the eleostearic acid of heat fused (or eleostearate), Resorcinol, catalyzer.Lead to nitrogen, stirring, be warming up to 100-130 ℃ gradually, reacted 2-3 hour.After reaction finished, the water that adding reactant 2-4 doubly measures in the reaction flask was heated to 80-90 ℃, stirred the hypsokinesis to be cooled layer that anhydrates 20-30 minute.So wash three times to remove unreacted Resorcinol.Product is brown sticky solid through washing, dewatering.Resorcinol importing rate can compare 1600cm in its infrared absorption spectrum by the ultimate analysis and the washing purifying front and back of purifying after product
-1Neighbouring phenyl ring absorption peak and 1700cm
-1Near carbonyl absorption peak obtains.In above system, add formalin, catalyzer and an amount of ethylene glycol monomethyl ether solvent, return at 60-100 ℃ earlier and heat up in a steamer reaction 1 hour, change water distilling apparatus again into, improve temperature of reaction simultaneously 100-120 ℃ of reaction 2-4 hour.Product is pale brown look solid.
[synthesis example 5-synthesis example 8]
The proportioning raw materials that provides according to table 2 in the four-hole reaction flask of agitator, thermometer is housed, adds eleostearic acid (or eleostearate), two Resorcinol formal, catalyzer, adds a small amount of solvent or solubilizing agent (logical nitrogen protection this moment) not.Heating, stir, be warming up to 120-150 ℃ gradually, react 2-4 hour, reaction finishes the back and adds the water that reactant 2-4 doubly measures, and is heated to 90-100 ℃, stirs 20-30 minute, cools off the hypsokinesis layer that anhydrates.So carry out three times to remove unreacted pair of Resorcinol formal and catalyzer.The product drying is pale brown look solid.The importing rate of two Resorcinol formals can be obtained by the absorption peak of phenyl ring and carbonyl in the infrared spectra after ultimate analysis and its water washing of comparison.
[synthesis example 9-synthesis example 10]
Reaction product by synthesis example 4, synthesis example 6 can directly be carried out aminolysis reaction.After finishing, synthesis example 4 reactions boil off most solvent so that next step aminolysis temperature can reach more than 140 ℃.After the reaction of synthesis example 6 is finished, directly in reaction system, add amine.Aminolysis reaction 140-160 ℃ of scope again carries out promptly accusing in 1-3 hour and finishes.Product is the khaki color solid.Basically carry out fully by visible its aminolysis reaction of the infrared spectra before and after the reaction.
Proportioning raw materials, reaction conditions and the product shape of table 1 synthesis example 1-synthesis example 4
| Project example preface synthesis example 1 synthesis example 2 synthesis examples 3 synthesis examples 4 | |
| The Resorcinol addition reaction | Reaction volume (g) eleostearic acid 278(1) 220(2 275(2.5 165(1.5 (mole number) ketone acid methyl esters 146 (0.5) 292 (1) Resorcinol 220(2 139(0.5 278(1)))))) |
| Catalyzer title tosic acid tricresyl phosphate Mono Chloro Acetic Acid oxalic acid percentage composition 0.5% 1% 1% 2% | |
| The reaction conditions temperature (℃) the 100-120 110-130 110-130 110-130 time (hour) 3323 | |
| The formolation reaction | Resorcinol importing rate 1.3-1.4 1.2-1.3 1.3-1.4 1.2-1.3 |
| Reaction volume formaldehyde (mole) 0.7 0.7 0.7 0.3 | |
| The only ether 1,000 440 570 500 of solvent ethylene glycol (g) | |
| The catalyzer title is to toluene acid iodide tricresyl phosphate Mono Chloro Acetic Acid oxalic acid percentage composition 0.2% 1% 0.5% 1% | |
| The reaction conditions temperature (℃) the 60-110 60-120 60-120 60-140 time (hour) 1+2 1+2 1+2 1+3 | |
| The product characteristics softening temperature (℃) 70-75 65-70 70-75 70-75 solvability is soluble in: acetone, ethanol, ethylene glycol monomethyl ether, dioxane, dimethyl formamide | |
Proportioning raw materials, reaction conditions and the product situation of table 2 synthesis example 5-synthesis example 8
| Project example preface synthesis example 5 synthesis examples 6 synthesis examples 7 synthesis examples | |
| Solvent (g) | Eleostearic acid 278 (1) methyl eleostearate 292(1) eleostearic acid ethyl ester 306(1) eleostearic acid-2-hydroxyl-3-chlorine propyl ester 371(1) two resorcinol formal 348 (1.5) 232 (1) 116 (0.5) 232 (1) ethylene glycol monoemethyl ether acetates 260 ethylene glycol monomethyl ethers 210 300 |
| Catalyzer (g) | Tosic acid 0.2% 0.5% phosphatase 11 % 0.5% |
| Reaction conditions | Temperature, (℃) the 120-140 120-160 120-140 120-140 time, (hour) 2 3.5 43 pairs of Resorcinols, four aldehyde 1.0-1.1 0.9-1.0, the 0.5 0.8-0.9 importing rate that contracts |
| Softening temperature 80-85 70-75 60-65 95-100 solvability is soluble in: acetone, ethanol, ethylene glycol monomethyl ether, dioxane, dimethyl formamide | |
The proportioning raw materials of table 3 synthesis example 9-synthesis example 10, reaction conditions and product situation project example preface synthesis example 9 synthesis examples 10
| Reaction volume (g) (mole number) | Eleostearic acid methyl esters-Resorcinol-four aldehyde synthesis example 4 product synthesis examples 6 product thanomin 122(2) diethanolamine 357(3) |
| Reaction conditions | Temperature (℃) the 140-150 140-160 time (hour) 23 |
| Product characters | Softening temperature 90-95 100-105 solvability is soluble in: acetone, ethanol, ethylene glycol ethyl ether dioxane, dimethyl formamide |
Claims (7)
1, a kind of synthetic method of elaeomargaric acid series resorcinol formaldehyde resin, the composition general formula of this resin can be expressed as:
R is that Resorcinol, T are eleostearic acid or eleostearate or eleostearic acid acid amides in the formula, n=0-300.Pre-treatments such as esterification comprising saponification, acid out and the eleostearic acid of tung oil is characterized in that:
(1) with eleostearic acid or eleostearate or the two miscellany and Resorcinol according to 1: the mol ratio of 1-5, the acid catalyst that adds the 0.01-2% of reactant weight, logical nitrogen, have or organic solvent-free in the presence of, at the Resorcinol affixture shown in the 60-140 ℃ of reaction 1-5 hour generation [2]:
R in the formula
1=H, CH
3, CH
2CH
3, CH (CH
3)
2Deng, X can be one of structure shown in (A), (B), (C), wherein (A), (B) they are major ingredient;
(2) be 1 with the Resorcinol affixture of above-mentioned eleostearic acid or eleostearate or the two mixture and formalin according to wherein Resorcinol and formaldehyde: the mol ratio of 0.25-0.75, add acid catalyst and an amount of organic solvent of reactant weight 0.01-5%, in 60-140 ℃ of reaction 2-6 hour, obtain the resorcinol formaldehyde resin of eleostearic acid or eleostearate or the two miscellany;
(3) with the eleostearate resorcinol formaldehyde resin that obtains in (2) and monoamine according to 1: the mol ratio of 0.5-5, in the presence of a small amount of organic solvent, in 140-170 ℃ of reaction 1-4 hour, obtain the resorcinol formaldehyde resin of eleostearic acid acid amides resorcinol formaldehyde resin or eleostearic acid acid amides and eleostearate miscellany.
2, according to the synthetic method of the described elaeomargaric acid series resorcinol formaldehyde resin of claim 1, the mol ratio that it is characterized in that the middle eleostearic acid of step (1) or eleostearic acid fat or the two miscellany and resorcin reaction is 1: 1.5-2.5, selecting the phosphoric acid of reactant gross weight 0.5-2% or the tosic acid of trichoroacetic acid(TCA) or oxalic acid or 0.2-1% for use is catalyzer, solubilizing agent not, logical nitrogen was 100-130 ℃ of reaction 2-4 hour.
3, according to claim 1 or 2 described elaeomargaric acid series resorcinol formaldehyde resin synthetic methods, it is characterized in that in the step (2), Resorcinol affixture and formalin are that to select the oxalic acid of 0.5-2% or the tosic acid of phosphoric acid or trichoroacetic acid(TCA) or 0.2-1% for use be catalyzer for 1: 0.5 mol ratio according to wherein Resorcinol and formaldehyde, add reactant weight 1-3 organic solvent doubly, earlier 60-100 ℃ of back flow reaction 1 hour, boil off the water in the system more gradually and improve temperature of reaction simultaneously, 100-120 ℃ of reaction 2-4 hour.
4,, it is characterized in that in the step (3), make eleostearic acid methyl esters resorcinol formaldehyde resin and thanomin or diethanolamine according to 1: the 1-3 mol ratio is reacted according to the synthetic method of claim 1 or 2 described elaeomargaric acid series resorcinol formaldehyde resins.
5, a kind of synthetic method of elaeomargaric acid series resorcinol formaldehyde resin, the composition system formula of this resin is:
R is a Resorcinol in the formula, R-(-CH
2-R)
mBe resorcinol formaldehyde oligopolymer, m=1-3, n=0-100.Comprising saponification, the acid out of tung oil, the esterification of eleostearic acid and make pre-treatments such as oligopolymer by Resorcinol and formaldehyde reaction.It is characterized in that:
(1) with eleostearic acid or eleostearate or the two mixture and resorcinol formaldehyde oligopolymer according to 1: the mol ratio of 0.25-2.5, the acid catalyst that adds the 0.01-5% of reactant weight, have or organic solvent-free in the presence of, 100-160 ℃ of reaction 2-6 hour, obtain the resorcinol formaldehyde resin of eleostearic acid shown in [3] or eleostearate or the two mixture;
(2) with the eleostearate resorcinol formaldehyde resin that obtains in (1) and monoamine according to 1: the mol ratio of 0.5-5, in the presence of a small amount of organic solvent, 140-170 ℃ of reaction 1-4 hour, obtain the resorcinol formaldehyde resin of eleostearic acid acid amides resorcinol formaldehyde resin or eleostearic acid acid amides and eleostearate miscellany.
6, according to the described elaeomargaric acid series resorcinol formaldehyde resin synthetic method of claim 5, it is characterized in that in the step (1), with eleostearic acid or eleostearate or the two mixture and two Resorcinol formals according to 1: the mol ratio of 0.5-1.5, with the tosic acid of reactant gross weight 0.2-1% or phosphoric acid or the trichoroacetic acid(TCA) of 0.5-2% is that catalyzer is in the presence of the organic solvent of 30-50%, 120-150 ℃ of reaction 2-4 hour.
7, according to claim 5 or 6 described elaeomargaric acid series resorcinol formaldehyde resin synthetic methods, it is characterized in that in the step (2), with eleostearic acid methyl esters resorcinol formaldehyde resin and thanomin or diethanolamine according to 1: the mol ratio of 1-3 is reacted.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103376 CN1067250A (en) | 1991-05-28 | 1991-05-28 | The synthetic method of elaeomargaric acid series resorcinol formaldehyde resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103376 CN1067250A (en) | 1991-05-28 | 1991-05-28 | The synthetic method of elaeomargaric acid series resorcinol formaldehyde resin |
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|---|---|
| CN1067250A true CN1067250A (en) | 1992-12-23 |
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ID=4906069
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107283B (en) * | 2005-01-25 | 2010-08-18 | 保土谷化学工业株式会社 | Ketone-modified resorcinol-formaldehyde resin |
| US8592480B2 (en) | 2006-07-21 | 2013-11-26 | Lyne Laboratories, Inc. | Liquid compositions of calcium acetate |
| CN105237720A (en) * | 2015-11-02 | 2016-01-13 | 华南农业大学 | PUA prepolymer containing double bond/phenolic hydroxyl double UV curing groups, as well as preparation method and application thereof |
| CN114409540A (en) * | 2022-02-17 | 2022-04-29 | 中国热带农业科学院南亚热带作物研究所 | Method for preparing tung oil alkylated derivatives by UV light/inorganic acid synergistic catalysis and its products and applications |
-
1991
- 1991-05-28 CN CN 91103376 patent/CN1067250A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107283B (en) * | 2005-01-25 | 2010-08-18 | 保土谷化学工业株式会社 | Ketone-modified resorcinol-formaldehyde resin |
| US8592480B2 (en) | 2006-07-21 | 2013-11-26 | Lyne Laboratories, Inc. | Liquid compositions of calcium acetate |
| US8591938B2 (en) | 2006-07-21 | 2013-11-26 | Lyne Laboratories, Inc. | Liquid compositions of calcium acetate |
| US9089528B2 (en) | 2006-07-21 | 2015-07-28 | Lyne Laboratories, Inc. | Liquid compositions of calcium acetate |
| CN105237720A (en) * | 2015-11-02 | 2016-01-13 | 华南农业大学 | PUA prepolymer containing double bond/phenolic hydroxyl double UV curing groups, as well as preparation method and application thereof |
| CN105237720B (en) * | 2015-11-02 | 2017-11-10 | 华南农业大学 | Containing the double UV curing groups PUA prepolymers of double bond/phenolic hydroxyl group and preparation method and application |
| CN114409540A (en) * | 2022-02-17 | 2022-04-29 | 中国热带农业科学院南亚热带作物研究所 | Method for preparing tung oil alkylated derivatives by UV light/inorganic acid synergistic catalysis and its products and applications |
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