CN111154053A - High-heat-resistance carboxyl phenolic resin and synthetic method thereof - Google Patents
High-heat-resistance carboxyl phenolic resin and synthetic method thereof Download PDFInfo
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- CN111154053A CN111154053A CN202010009712.5A CN202010009712A CN111154053A CN 111154053 A CN111154053 A CN 111154053A CN 202010009712 A CN202010009712 A CN 202010009712A CN 111154053 A CN111154053 A CN 111154053A
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- aldehyde
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 40
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 38
- -1 carboxyl phenolic resin Chemical compound 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 25
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 15
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 230000001502 supplementing effect Effects 0.000 claims description 11
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 10
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 claims description 6
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 6
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 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 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 5
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 4
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- BYHDDXPKOZIZRV-UHFFFAOYSA-N 5-phenylpentanoic acid Chemical compound OC(=O)CCCCC1=CC=CC=C1 BYHDDXPKOZIZRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- XPKFJIVNCKUXOI-UHFFFAOYSA-N formaldehyde;2-hydroxybenzoic acid Chemical compound O=C.OC(=O)C1=CC=CC=C1O XPKFJIVNCKUXOI-UHFFFAOYSA-N 0.000 claims 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 12
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 150000003384 small molecules Chemical class 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229960003424 phenylacetic acid Drugs 0.000 description 2
- 239000003279 phenylacetic acid Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
Abstract
The invention discloses a high heat resistance carboxyl phenolic resin and a synthesis method thereof, belonging to the technical field of functional polymer material preparation. The structural general formula of the high-heat-resistance carboxyl phenolic resin synthesized by the invention is
Wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, and R is H, phenyl or C1-C9 alkyl. The synthetic method is that the phenol compound, p-aldehyde group benzoic acid, formaldehyde water solution and catalyst are processed with polycondensation reaction to obtain the product. The phenolic resin produced by the invention has the weight average molecular weight of 8000-.
Description
Technical Field
The invention relates to the technical field of functional polymer preparation, in particular to high-heat-resistance carboxyl phenolic resin prepared by taking p-aldehyde benzoic acid as a raw material.
Background
The linear phenolic resin belongs to thermoplastic resin, and has important application value in the fields of paint, electronics, printing ink, photoresist and the like due to the easily available raw materials, low price, good molding manufacturability, regular structure and excellent mechanical property and heat resistance. However, with the development of technology, the process is continuously improved, and higher requirements are also made on the performance of the material. Traditional phenol novolac resins are not suitable for some occasions with high requirement on heat resistance, and how to improve the heat resistance of phenol novolac resins has become a key development direction in the industry.
The phenolic resin has a structure with a large number of aromatic rings, high bond energy between atoms and high cohesive energy between molecular chains, so that the phenolic resin shows remarkable heat resistance, and if the thermal property needs to be further improved, one of the methods is chemical modification. The phenolic resin has the weakness that phenolic hydroxyl and methylene are easy to oxidize, so that the protection of the hydroxyl and the methylene is an important way for improving the heat resistance of the phenolic resin, and the main method can be as follows: 1. the molecular weight of the resin is improved, longer molecular chain segments are obtained, the entanglement among the chain segments is increased, the chain cluster size is increased, the free moving capacity of each molecule is reduced, meanwhile, the phenolic hydroxyl groups with larger proportion are embedded in the chain clusters, and the oxidation speed of the phenolic hydroxyl groups is reduced. 2. The proportion of the heat-resistant structure of benzene ring is increased in the resin, and the heat-resistant group is increased. 3. The proportion of methylene on the main chain is reduced, thereby increasing the oxidation resistance. Patent CN101696256A discloses a method for introducing carboxyl into phenolic resin, i.e. selecting phenol with carboxyl as polymerization monomer, but the molecular weight of the phenolic resin synthesized in the patent is lower, below 5000g/mol, and there is no mention of increasing the proportion of benzene ring and reducing the proportion of methylene group on main chain to improve the heat resistance of the resin.
Disclosure of Invention
The invention aims to introduce more benzene ring structures, reduce the proportion of methylene and improve the molecular weight of resin in the traditional linear thermoplastic phenolic resin so as to improve the heat resistance of the resin, and simultaneously introduce carboxyl groups so as to ensure the alkali solubility of the resin, thereby obtaining the high-molecular-weight high-heat-resistance carboxyl phenolic resin.
The technical scheme of the invention is as follows:
the invention provides a high heat resistance carboxyl phenolic resin, the structural formula is as follows:
wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, and R is H, phenyl or C1-C9 alkyl. Further, the weight average molecular weight range is 8000-.
The invention also provides a preparation method of the high heat resistance carboxyl phenolic resin, which comprises the following steps:
adding p-aldehyde benzoic acid and an organic solvent into a reaction container, stirring, heating to 80-120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding a phenol compound, slowly dropwise adding a catalyst aqueous solution into the reaction container, reacting for 2-10h, then slowly dropwise adding a formaldehyde aqueous solution into the reaction container, and continuing to react for 3-10 h;
adding pure water into the reaction vessel, setting the oil bath temperature between 40 and 80 ℃, stirring for half an hour, standing for layering, pouring out the upper-layer water solution, continuously supplementing the same amount of pure water, continuously stirring, standing for layering, and pouring out the water layer; repeating the water washing step for 3-6 times;
heating to 180 ℃ to distill moisture and organic solvent, heating to 200 ℃, and carrying out vacuum filtration to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the high heat-resistant carboxyl phenolic resin.
Further, the p-aldehyde benzoic acid is one or more of p-aldehyde benzoic acid, p-aldehyde phenylacetic acid, p-aldehyde phenylpropionic acid, p-aldehyde phenylbutyric acid and p-aldehyde phenylpentanoic acid.
Further, the organic solvent is one or more of ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether, ethyl lactate, N-dimethylformamide, N-dimethylacetamide and gamma-butyrolactone.
Further, the phenol compound is one or more of phenol, m-cresol, p-cresol, o-cresol, 3, 5-xylenol, 3, 4-xylenol, 2,3, 5-trimethylphenol, p-tert-butylphenol and naphthol.
Further, the catalyst is one or more of p-toluenesulfonic acid, oxalic acid, hydrochloric acid, trichloroacetic acid and phosphoric acid, and the weight of the catalyst accounts for 1% -3% of that of the phenol compounds.
Further, the molar ratio of the phenol compound to the p-aldehyde benzoic acid is 1: 0.05-1:0.3.
Further, the concentration of the formaldehyde aqueous solution is 36-37%, and the molar ratio of the phenol compound to the formaldehyde is 1: 0.7-1:0.85.
The invention has the beneficial effects that:
1. the invention selects aldehyde with a carboxyl benzene ring structure, such as p-aldehyde benzoic acid, to partially replace formaldehyde to participate in the condensation polymerization reaction of the phenolic resin, has lower cross-linking activation energy of carboxyl compared with phenolic hydroxyl with epoxy curing agents, simplifies the processing technology difficulty, and has stronger ionization ability with alkali liquor, thereby greatly improving the alkali solubility of the resin. The carboxyl-containing linear phenolic resin with large molecular weight is synthesized, and is applied to the fields of electronics and coatings, so that the use amount of a curing agent can be reduced, and the processing energy consumption can be reduced. High alkali solubility, high imaging speed and sensitivity, and good application in printing, printing ink and photoresist fields.
2. The p-aldehyde benzoic acid has a benzene ring structure and is bonded to the inside of the resin, so that the proportion of the benzene ring, namely the heat-resistant group in the resin can be improved.
3. The aldehyde group on the aldehyde benzoic acid can replace formaldehyde to participate in polymerization, so that in a linear structure, the proportion of methylene on a main chain is reduced, and a triphenyl structure is replaced, so that the rigidity and the heat resistance are improved.
Drawings
FIG. 1 is a DSC chart of a high heat-resistant carboxyl phenol resin synthesized in example 6 of the present invention;
FIG. 2 is a DSC chart of the high heat-resistant carboxy phenol resin synthesized in example 8 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Polymerization of S01: adding 0.05mol of p-aldehyde benzoic acid and 15ml of ethylene glycol methyl ether acetate into a 1L four-mouth bottle provided with a stirrer, a condenser pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding 0.7mol of m-cresol and 0.3mol of p-cresol, slowly dropwise adding an oxalic acid aqueous solution with the mass fraction of 1% of a phenol compound into the four-mouth bottle, reacting for 2 hours, then slowly dropwise adding 0.85mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing to react for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 40 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 3 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 2
Polymerization of S01: adding 0.1mol of p-aldehyde phenylacetic acid and 30ml of ethylene glycol ethyl ether acetate into a 1L four-mouth bottle provided with a stirrer, a condenser pipe, a constant pressure dropping funnel and a thermometer, starting stirring, heating to 110 ℃ until the p-aldehyde phenylacetic acid is dissolved, then adding 0.6mol of phenol and 0.4mol of o-cresol, slowly dropwise adding a p-toluenesulfonic acid aqueous solution with the mass fraction of 1.5% of phenol compound into the four-mouth bottle, reacting for 4 hours, then slowly dropwise adding 0.85mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 50 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 3 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 3
Polymerization of S01: adding 0.15mol of p-aldehyde phenylpropionic acid and 45ml of ethylene glycol methyl ether into a 1L four-mouth bottle provided with a stirrer, a condenser tube, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 100 ℃ until the p-aldehyde phenylpropionic acid is dissolved, then adding 0.5mol of 3, 5-diphenol and 0.5mol of 3, 4-xylenol, slowly dropping a hydrochloric acid aqueous solution with 2 mass percent of phenol compounds into the four-mouth bottle, reacting for 5 hours, then slowly dropping 0.8mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 60 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 4 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 4
Polymerization of S01: adding 0.2mol of p-aldehyde phenylbutyric acid and 50ml of ethyl lactate into a 1L four-mouth bottle provided with a stirrer, a condenser pipe, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 90 ℃ until the p-aldehyde phenylbutyric acid is dissolved, then adding 0.5mol of m-cresol and 0.5mol of p-tert-butylphenol, slowly dropwise adding a trichloroacetic acid aqueous solution with the mass fraction of 2.5% of a phenol compound into the four-mouth bottle, reacting for 8 hours, then slowly dropwise adding 0.8mol of a formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 70 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 5 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 5
Polymerization of S01: adding 0.25mol of p-aldehyde benzovaleric acid and 50ml of N, N-dimethylformamide into a 1L four-mouth bottle provided with a stirrer, a condenser tube, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 80 ℃ until the p-aldehyde benzovaleric acid is dissolved, then adding 0.2mol of naphthol and 0.8mol of 2,3, 5-trimethylphenol, slowly dropping a phosphoric acid aqueous solution with 3 mass percent of phenol compounds into the four-mouth bottle, reacting for 8 hours, then slowly dropping 0.8mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 80 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 6 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 6
Polymerization of S01: adding 0.3mol of p-aldehyde benzoic acid and 50ml of N, N-dimethylacetamide into a 1L four-mouth bottle provided with a stirrer, a condenser tube, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding 0.5mol of m-cresol and 0.5mol of p-cresol, slowly dropwise adding an oxalic acid aqueous solution with the mass fraction of 3% of a phenol compound into the four-mouth bottle, reacting for 10 hours, then slowly dropwise adding 0.7mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 50 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 3 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 7
Polymerization of S01: adding 0.25mol of p-aldehyde benzoic acid and 50ml of dioxane into a 1L four-mouth bottle provided with a stirrer, a condenser tube, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 100 ℃ until the p-aldehyde benzoic acid is dissolved, then adding 1mol of m-cresol, slowly dropwise adding an oxalic acid aqueous solution with the mass fraction of 2.5% of phenol compounds into the four-mouth bottle, reacting for 2 hours, then slowly dropwise adding 0.7mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 5 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 50 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 6 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 8
Polymerization of S01: adding 0.1mol of p-aldehyde benzoic acid and 30ml of gamma-butyrolactone into a 1L four-mouth bottle provided with a stirrer, a condenser tube, a constant-pressure dropping funnel and a thermometer, starting stirring, heating to 120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding 0.8mol of m-cresol and 0.2mol of p-cresol, slowly dropping an oxalic acid aqueous solution with the mass fraction of 3% of phenol compound into the four-mouth bottle, reacting for 10 hours, then slowly dropping 0.85mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 10 hours.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 50 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 6 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
Example 9
Polymerization of S01: adding 0.05mol of p-aldehyde benzoic acid and 15ml of ethylene glycol methyl ether acetate into a 1L four-mouth bottle provided with a stirrer, a condenser pipe, a constant pressure dropping funnel and a thermometer, starting stirring, heating to 120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding 0.9mol of 3, 5-xylenol and 0.1mol of p-tert-butylphenol, slowly dropwise adding an oxalic acid aqueous solution with the mass fraction of 1% of phenol compounds into the four-mouth bottle, reacting for 6h, then slowly dropwise adding 0.85mol of formaldehyde aqueous solution into the four-mouth bottle, and continuing the reaction for 9 h.
S02 water washing: adding 200ml of pure water into a four-mouth bottle through a constant pressure funnel, setting the temperature of an oil bath at 50 ℃, stirring for half an hour, standing for layering, pouring out upper-layer water liquid, continuously supplementing pure water with the same amount, continuously stirring, standing for layering, and pouring out a water layer. The above water washing step was repeated 6 times.
S03 removal of small molecules: heating to 180 deg.C, distilling water and specific organic solvent, heating to 200 deg.C, and vacuum filtering to remove residual monomer phenol. Pouring out the molten resin in the four-mouth bottle to obtain the high-heat-resistance carboxyl phenolic resin.
The examples 1-9 were tested for performance as shown in the following table:
table 1 examples 1-9 performance test results
Note: the free phenol is obtained by a method for measuring the content of the free phenol in the phenolic resin according to the gas chromatography of GB/T30773-2014;
testing the weight average molecular weight: tosoh Biotechnology Ltd, model HLC-8320 GPC, the mobile phase is chromatographic pure THF, the test temperature is 35 ℃, the solvent flow rate is 1.0mL/min, the standard sample is polystyrene (PSt);
alkali dissolution rate test: the high heat-resistant carboxyl phenolic resin of the example is dissolved in propylene glycol methyl ether acetate solution, spin-coated on a silicon chip, baked for 90s at 100 ℃, and cooled. The number of revolutions of the spin coating was adjusted to finally obtain a resin film of 5um thickness, and the total time required for dissolution was measured by a Lith tech instrument, and the required data was obtained at an alkali dissolution rate ═ film thickness/dissolution time.
And (3) testing the glass transition temperature: model 822e differential scanning calorimeter from Mettler-Toledo, Switzerland, N2The flow rate is 50mL/min, the heating rate is 20 ℃/min, the first heating is 40-100 ℃, the second heating temperature scanning range is 40-200 ℃, the glass transition temperature (Tg) of the polymer is measured, and a second heating curve is used for testing the Tg.
As shown in the above table, the novolak resins synthesized in examples 1-9 have the characteristics of less free phenol, high molecular weight, good heat resistance, and high alkali dissolution rate, and have excellent application values in the fields of printing, electronics, coatings, inks, photoresists, and the like.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (9)
1. A high heat-resistant carboxyl phenolic resin is characterized in that: the structural formula is as follows:
wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, and R is H, phenyl or C1-C9 alkyl.
2. The highly heat-resistant carboxyl phenol resin according to claim 1, characterized in that: the weight average molecular weight range is 8000-.
3. A preparation method of high heat resistance carboxyl phenolic resin is characterized in that: the method comprises the following steps:
adding p-aldehyde benzoic acid and an organic solvent into a reaction container, stirring, heating to 80-120 ℃ until the p-aldehyde benzoic acid is dissolved, then adding a phenol compound, slowly dropwise adding a catalyst aqueous solution into the reaction container, reacting for 2-10h, then slowly dropwise adding a formaldehyde aqueous solution into the reaction container, and continuing to react for 3-10 h;
adding pure water into the reaction vessel, setting the oil bath temperature between 40 and 80 ℃, stirring for half an hour, standing for layering, pouring out the upper-layer water solution, continuously supplementing the same amount of pure water, continuously stirring, standing for layering, and pouring out the water layer; repeating the water washing step for 3-6 times;
heating to 180 ℃ to distill moisture and organic solvent, heating to 200 ℃, and carrying out vacuum filtration to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the high heat-resistant carboxyl phenolic resin.
4. The method for preparing high heat-resistant carboxyl phenol resin according to claim 3, wherein the p-aldehyde benzoic acid is one or more of p-aldehyde benzoic acid, p-aldehyde phenylacetic acid, p-aldehyde phenylpropionic acid, p-aldehyde phenylbutyric acid and p-aldehyde phenylpentanoic acid.
5. The method for preparing carboxyl phenol-formaldehyde resin with high heat resistance as claimed in claim 3, wherein the organic solvent is one or more of ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether, ethyl lactate, N-dimethylformamide, N-dimethylacetamide and gamma-butyrolactone.
6. The method for preparing carboxyl phenol-formaldehyde resin with high heat resistance according to claim 3, wherein the phenol compound is one or more of phenol, m-cresol, p-cresol, o-cresol, 3, 5-xylenol, 3, 4-xylenol, 2,3, 5-trimethylphenol, p-tert-butylphenol, and naphthol.
7. The method for preparing carboxyl phenolic resin with high heat resistance as claimed in claim 3, wherein the catalyst is one or more of p-toluenesulfonic acid, oxalic acid, hydrochloric acid, trichloroacetic acid and phosphoric acid, and the weight of the catalyst accounts for 1% -3% of that of the phenolic compound.
8. The method for preparing a high heat-resistant carboxyl phenol resin according to claim 3, wherein the molar ratio of the phenol compound to the p-aldehyde benzoic acid is 1: 0.05-1:0.3.
9. The method for preparing a carboxyl phenol-formaldehyde resin with high heat resistance according to claim 3, wherein the concentration of the formaldehyde aqueous solution is 36 to 37 percent, and the molar ratio of the phenol compound to the formaldehyde is 1: 0.7-1:0.85.
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| CN101693758A (en) * | 2009-10-30 | 2010-04-14 | 北京师范大学 | Synthesis of carboxylic phenol resin active ester and etherate |
| CN101696256A (en) * | 2009-10-30 | 2010-04-21 | 北京师范大学 | Hydroxyl phenolic resin and synthesis method thereof |
| WO2019239784A1 (en) * | 2018-06-13 | 2019-12-19 | Dic株式会社 | Phenolic novolac resin, method for manufacturing same, photosensitive composition, resist material, and resist film |
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| CN101693758A (en) * | 2009-10-30 | 2010-04-14 | 北京师范大学 | Synthesis of carboxylic phenol resin active ester and etherate |
| CN101696256A (en) * | 2009-10-30 | 2010-04-21 | 北京师范大学 | Hydroxyl phenolic resin and synthesis method thereof |
| WO2019239784A1 (en) * | 2018-06-13 | 2019-12-19 | Dic株式会社 | Phenolic novolac resin, method for manufacturing same, photosensitive composition, resist material, and resist film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114671988A (en) * | 2020-12-24 | 2022-06-28 | 上海彤程电子材料有限公司 | Multifunctional group-containing substituted benzyl phenolic aldehyde polymer and preparation method and application thereof |
| CN114671988B (en) * | 2020-12-24 | 2023-10-17 | 上海彤程电子材料有限公司 | Multifunctional group-containing substituted benzyl phenolic polymer and preparation method and application thereof |
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