CN114656376A - Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method - Google Patents
Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method Download PDFInfo
- Publication number
- CN114656376A CN114656376A CN202210383316.8A CN202210383316A CN114656376A CN 114656376 A CN114656376 A CN 114656376A CN 202210383316 A CN202210383316 A CN 202210383316A CN 114656376 A CN114656376 A CN 114656376A
- Authority
- CN
- China
- Prior art keywords
- cardanol
- reaction
- phenol resin
- dicyclopentadiene
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 61
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- -1 cardanol modified dicyclopentadiene Chemical class 0.000 title claims abstract description 26
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 55
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006277 sulfonation reaction Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 27
- 239000007795 chemical reaction product Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 2
- 238000003303 reheating Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 26
- 229920005989 resin Polymers 0.000 abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001568 phenolic resin Polymers 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005844 autocatalytic reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of phenolic resin products, in particular to a method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting a bisphenol method. Excessive cardanol and concentrated sulfuric acid are subjected to sulfonation reaction to generate sulfonated cardanol, the sulfonated cardanol can be used as an autocatalyst, the reaction with phenol can be autocatalyzed, cardanol, phenol and dicyclopentadiene can be catalyzed to be condensed to generate cardanol modified dicyclopentadiene phenol resin, and the reaction process is green and environment-friendly. Meanwhile, the sulfonated cardanol is introduced, so that the phenolic hydroxyl group on the dicyclopentadiene phenol resin molecule and hydrogen atoms on other molecular structures can generate nucleophilic substitution reaction, methylene or dibenzyl ether is promoted to be generated, the crosslinking and curing of the molecule are further promoted, the degree of polymerization of the reaction of dicyclopentadiene and phenol is reduced, the water absorption resistance of the resin is improved, and the insulating property, the toughness, the acid resistance, the heat resistance, the corrosion resistance and other properties of the resin are improved.
Description
Technical Field
The invention relates to the technical field of phenolic resin products, in particular to a method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting a bisphenol method.
Background
Cardanol is rich in source, nontoxic, structurally similar to phenol, and has long aliphatic chain. The phenolic resin prepared by partially replacing phenol with cardanol can obviously improve the toughness of the resin due to the introduction of long-chain alkane groups. Research shows that the comprehensive performance of the phenolic resin prepared by replacing phenol with cardanol can be improved, and the material cost is greatly reduced (Yannwei et al. synthesis and application research of cardanol/cashew nut shell oil modified phenolic resin [ J ]. thermosetting resin 2020, 25(5): 21-26; Liuyang. preparation and performance research of boron-cardanol modified phenolic resin [ D ]. Wuhan university of science and technology 2015 ]).
The dicyclopentadiene phenol resin is an important raw material of semiconductor sealing materials, and can be used for producing adhesives, antioxidants, laminated plates, epoxy resin modifiers and the like. The molecular structure of the dicyclopentadiene-phenol resin contains phenolic hydroxyl, benzene ring, five-membered ring and six-membered ring, and the resin has good heat resistance, acid and alkali resistance, friction resistance, chemical reaction performance and electrical insulation performance. Can be used in paint manufacturing industry, and can also be used in epoxy resin curing agents, printed circuit boards, semiconductor sealants and the like.
However, in previous studies, BF has often been used for the reaction of dicyclopentadiene with phenol3·Et2O, methanesulfonic acid and the like are used as catalysts, the traditional liquid acid catalysts have the defects of strong corrosivity, non-recycling, poor economy and the like, and the adoption of the catalysts can generate a large amount of wastewater in the reaction process and does not meet the requirement of green production (Sun Haojia and the like. the new synthesis process of dicyclopentadiene phenol resin [ J]Applied chemistry, 2011, 28(06):629-633)。
Disclosure of Invention
Based on the technical problems pointed out in the background technology part, the sulfonated cardanol is used as the catalyst, the catalyst can catalyze the reaction of the cardanol and the phenol with the dicyclopentadiene, the cardanol and the phenol can be catalyzed to react with the dicyclopentadiene, no waste water is generated in the catalytic reaction process, and the process is green and environment-friendly. Meanwhile, the cardanol structure containing sulfonate groups is introduced into dicyclopentadiene phenol resin, the degree of polymerization of reaction of dicyclopentadiene and phenol is reduced, the performance of the resin is improved, the synthesized modified resin has good heat resistance, corrosion resistance, electric insulation and water absorption resistance, the addition of sulfonate groups can greatly promote the crosslinking and curing of the dicyclopentadiene phenol resin, the curing temperature is reduced, and the curing rate is greatly improved.
In order to achieve the purpose, the invention provides a method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting a bisphenol method, which comprises the following specific steps:
(1) adding cardanol into a reactor, heating to a reaction temperature under stirring, dropwise adding concentrated sulfuric acid, after dropwise adding, keeping the temperature for reacting for a certain time, and cooling after the reaction is finished to obtain a reaction product A;
wherein the mass ratio of concentrated sulfuric acid to cardanol is 1: 10-1: 40, the reaction temperature is 50-60 ℃, the dropping time of concentrated sulfuric acid is 0-1 h, and the heat preservation reaction time is 0.5-3 h.
The cardanol in the step (1) is in large excess, so that the obtained reaction product A does not contain unreacted concentrated sulfuric acid, but contains sulfonated and non-sulfonated cardanol, wherein the sulfonated cardanol structure contains a sulfonic acid group with strong acidity, so that the cardanol has an autocatalytic effect, can be reacted with phenol by autocatalysis, and can also be used for catalyzing the reaction of cardanol, phenol and dicyclopentadiene.
(2) Heating the reaction product A, adding phenol, and reacting the product A with phenol at the temperature to obtain a product B;
wherein the temperature of the reaction product A is 120-150 ℃, and the reaction time is 1-4 h; reaction product A: the mass ratio of phenol is 1: 10-3: 10.
The reaction product B generated in the step (2) also contains a sulfonic acid group with stronger acidity, and can continuously catalyze the further reaction with dicyclopentadiene.
(3) After the reaction is finished, cooling the reaction product B to 60 ℃, stirring at the temperature, dropwise adding dicyclopentadiene into the reaction product B, keeping the temperature for reacting for a certain time after dropwise adding, heating to the reaction temperature for reacting, heating to the certain temperature after the reaction is finished, decompressing and dephenolizing, and cooling to obtain the cardanol modified dicyclopentadiene phenol resin;
wherein the reaction product B in step (3): the mass ratio of the dicyclopentadiene to the dicyclopentadiene is 1: 1-6: 1, the dripping time of the dicyclopentadiene is 0-1 h, the heat preservation temperature is 80-90 ℃, and the heat preservation time is 1-3 h;
the reaction temperature of the dicyclopentadiene and the reaction product B is 100-120 ℃, and the reaction time is 2-5 h.
The vacuum degree of the decompression dephenolization is less than-0.09 MPa, the temperature is 180-200 ℃, and the time is 2-3 h.
The invention adopts a bisphenol method to synthesize cardanol modified dicyclopentadiene phenol resin. Firstly, excessive cardanol reacts with concentrated sulfuric acid to generate sulfonated cardanol, then the sulfonated cardanol reacts with phenol, and the reaction product continuously reacts with dicyclopentadiene to obtain the cardanol modified dicyclopentadiene phenol resin. The sulfonated cardanol has an autocatalytic effect, so that no other catalyst is needed to be added in the reaction.
Compared with the background technology, the invention achieves the technical progress that:
according to the invention, the sulfonated cardanol with an autocatalysis effect is used as a modifier, and a cardanol long-chain structure containing a sulfonate group can be introduced into dicyclopentadiene phenol resin without adding other catalysts, so that the toughness and heat resistance of the resin are greatly improved. At the same time, it can replace BF3·Et2O, methanesulfonic acid and the like, catalyzes the alkylation reaction of phenol and dicyclopentadiene, can be removed without washing with water, is simple to operate, is green and environment-friendly, and has strong economic benefit.
The method has the following specific advantages:
1. the reaction raw materials are wide, cardanol is used as the raw material, the source is rich, toxicity is avoided, and the structure of the cardanol is similar to that of phenol.
2. The sulfonated cardanol has a sulfonic group with strong acidity, can be subjected to autocatalysis reaction with phenol without adding other acidic catalysts, and is simple to operate.
3. The sulfonated cardanol is used as a catalyst and can replace BF3·Et2O, methanesulfonic acid and the like catalyze the reaction of dicyclopentadiene and phenol, so that the steps of water washing and the like are omitted, the generation of waste water is reduced, and the method is more green and environment-friendly.
4. The sulfonated cardanol is used as a modifier, the structure of the cardanol can be introduced into dicyclopentadiene phenol resin, and the flexibility, heat resistance and electrical insulation of the resin are improved.
5. The sulfonic acid group structure is introduced into the structure of the dicyclopentadiene phenol resin, so that the resin can be promoted to be crosslinked and cured, the temperature required by curing is reduced, and the curing speed is improved.
6. The reaction condition is relatively mild, and the operation is simple and convenient.
7. No waste water discharge in the synthesis process, and belongs to an environment-friendly process route.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present invention.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
The cardanol related by the invention has the following structure:
the reaction equation of cardanol and concentrated sulfuric acid related by the invention is as follows:
the reaction equation of the sulfonated cardanol and phenol is as follows:
the reaction equation of cardanol, sulfonated cardanol and phenol related by the invention is as follows:
the reaction equation of the product and dicyclopentadiene is:
example 1
Taking 400g of cardanol in a four-neck flask, stirring and heating to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 200g of the reaction product A to 130 ℃, adding 1000g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Example 2
Taking 400g of cardanol in a four-neck flask, stirring and heating to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 200g of the reaction product A to 130 ℃, adding 1000g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 5 hours at 120 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Example 3
Taking 400g of cardanol in a four-neck flask, stirring and heating to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 200g of the reaction product A to 130 ℃, adding 1000g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 100 ℃, and stirring and reacting for 2 hours at 100 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Example 4
Taking 400g of cardanol in a four-neck flask, stirring and heating to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 200g of the reaction product A to 130 ℃, adding 700g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Example 5
Taking 400g of cardanol in a four-neck flask, stirring and heating to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 100g of the reaction product A to 130 ℃, adding 1000g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Example 6
200g of cardanol is taken in a four-neck flask, stirred and heated to 50 ℃; adding 10g of concentrated sulfuric acid into a constant-pressure dropping funnel, and dropping the concentrated sulfuric acid into the cardanol within 50 min; after the dropwise addition is finished, reacting at a constant temperature of 55 ℃ for 2 hours, and cooling after the reaction is finished to obtain a sulfonated product A;
heating 200g of the reaction product A to 130 ℃, adding 1000g of phenol, and pre-reacting for 3 hours at 130 ℃; after the pre-reaction is finished, cooling to 60 ℃, dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel under stirring, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, heating to 180 ℃, decompressing and dephenolizing for 2 hours, and finally cooling and discharging to obtain the cardanol modified dicyclopentadiene phenol resin.
Comparative example 1
400g cardanol and 1000g phenol are taken to be put into a reactor, and 6.5ml BF is added3·Et2O, stirring at 130 DEG CReacting for 3 hours; after the reaction is finished, cooling the product to 60 ℃, stirring, and then dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, washing the reaction product by using hot deionized water until a water layer is neutral, heating the reaction product to 180 ℃, decompressing and dephenolizing the reaction product for 2 hours, and finally cooling and discharging the reaction product to obtain the cardanol modified dicyclopentadiene phenol resin.
Comparative example 2
Taking 400g of cardanol and 1000g of phenol, adding 17.5g of p-toluenesulfonic acid into a reactor, and reacting for 3 hours at 130 ℃ while stirring; after the reaction is finished, cooling the product to 60 ℃, stirring, and then dropwise adding 100g of dicyclopentadiene by using a constant-pressure dropping funnel, wherein the dropwise adding time is 1h, and the dropwise adding temperature is controlled to be 80-90 ℃; after the dropwise addition is finished, keeping the temperature at 80 ℃ for reaction for 2 hours; continuously stirring and heating to 120 ℃, and stirring and reacting for 2 hours at 120 ℃; and after the reaction is finished, washing the reaction product by using hot deionized water until a water layer is neutral, heating the reaction product to 180 ℃, decompressing and dephenolizing the reaction product for 2 hours, and finally cooling and discharging the reaction product to obtain the cardanol modified dicyclopentadiene phenol resin.
The following examples of the present invention and comparative examples of the solid resin of the reddish brown transparent resin were subjected to the performance test, and the test results are shown in Table 1.
TABLE 1 resin Performance test of examples and comparative examples
| Numbering | Softening point/. degree.C | Rotational viscosity/P | Speed of polymerization/s | Free phenol/%) |
| Example 1 | 96.8 | 2.88 | 90 | 0.01 |
| Example 2 | 100.8 | 2.91 | 97 | 0.02 |
| Example 3 | 94.8 | 2.19 | 78 | 0.04 |
| Example 4 | 95.9 | 2.65 | 83 | 0.04 |
| Example 5 | 93.8 | 2.03 | 71 | 0.01 |
| Example 6 | 91.3 | 1.77 | 68 | 0.03 |
| Comparative example 1 | 90.6 | 1.62 | 62 | 0.03 |
| Comparative example 2 | 88.6 | 1.41 | 56 | 0.04 |
With the help of TG analysis method, the change of heat resistance of the resins of example 1 and comparative example is discussed, the weight loss temperature of the resins with different percentages and the carbon residue amount at different temperatures are studied, and the test results are shown in Table 2.
TABLE 2 results of thermogravimetric testing of different resins
| Numbering | 2% weight loss temperature/. degree.C | 5% weight loss temperature/. degree.C | 300 ℃ carbon residue/%) | 600 ℃ carbon residue/%) |
| Example 1 | 388 | 436 | 90.7 | 60.1 |
| Example 2 | 373 | 424 | 86.5 | 54.9 |
| Example 3 | 366 | 414 | 85.6 | 53.4 |
| Example 4 | 371 | 421 | 86.2 | 54.2 |
| Example 5 | 362 | 401 | 84.8 | 53.1 |
| Example 6 | 360 | 398 | 84.0 | 52.2 |
| Comparative example 1 | 356 | 394 | 83.6 | 52.9 |
| Comparative example 2 | 302 | 356 | 81.5 | 51.7 |
Of the above resins, the 2% and 5% weight loss temperatures of example 1 were the highest, at 388 ℃ and 436 ℃, respectively; the char yields of the resin of example 1 at 300 ℃ and 600 ℃ were 90.7% and 60.1%, respectively, which are significantly higher than the resins of comparative examples 1 and 2. The above results show that the high temperature stability of the sulfonated cardanol modified dicyclopentadiene phenol resin is significantly improved.
The shear strength of the resins of examples and comparative examples 1 and 2 was investigated and the results are shown in Table 3.
TABLE 3 shear Strength of different resins
| Numbering | Shear strength at room temperature/MPa | Strength at 150 ℃ per MPa | Strength at 250 ℃ per MPa | Strength at 300 ℃ per MPa |
| Example 1 | 7.31 | 6.81 | 6.12 | 5.36 |
| Example 2 | 6.94 | 6.11 | 5.78 | 5.11 |
| Example 3 | 6.27 | 5.72 | 5.03 | 4.89 |
| Example 4 | 6.79 | 6.04 | 5.69 | 5.04 |
| Example 5 | 6.02 | 5.33 | 4.89 | 4.44 |
| Example 6 | 5.92 | 5.26 | 4.71 | 4.28 |
| Comparative example 1 | 5.89 | 5.11 | 4.52 | 4.05 |
| Comparison ofExample 2 | 4.45 | 3.41 | 3.02 | 2.49 |
Of the above resins, example 1 had shear strengths at room temperature, 150 ℃, 250 ℃ and 300 ℃ of 7.31MPa, 6.81MPa, 6.12MPa and 5.36MPa, respectively, which were significantly higher than the two comparative resins at different temperatures. The above results show that the long-chain alkyl in the sulfonated cardanol structure has a toughening effect on the resin, so that the shear strength of the modified resin is improved, and the modified resin shows good high-temperature adhesion.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (8)
1. A method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting a bisphenol method is characterized by comprising the following steps: and carrying out sulfonation reaction on excessive cardanol and concentrated sulfuric acid, reacting the sulfonated product with phenol, adding dicyclopentadiene into the reaction system, and reacting to obtain the cardanol modified dicyclopentadiene phenol resin.
2. The method for synthesizing the cardanol modified dicyclopentadiene phenol resin by using the bisphenol method according to claim 1, characterized by comprising the following steps:
(1) adding cardanol into a reactor, stirring and heating to a reaction temperature, dropwise adding concentrated sulfuric acid, after dropwise adding, carrying out heat preservation reaction, finishing the reaction, and cooling to obtain a reaction product A;
(2) adding the product A into a reactor, stirring and heating, adding phenol, and reacting to obtain a product B;
(3) after the reaction is finished, cooling the product B to 60 ℃, dropwise adding dicyclopentadiene under stirring, preserving heat for reaction after dropwise adding is finished, and then heating for reaction; and after the reaction is finished, heating and decompressing to remove phenol to obtain the sulfonated cardanol modified dicyclopentadiene phenol resin.
3. The method for synthesizing the cardanol-modified dicyclopentadiene phenol resin by using the bisphenol method according to claim 2, wherein the mass ratio of the concentrated sulfuric acid to the cardanol in step (1) is 1:10 to 1:40, the reaction temperature is 50 to 60 ℃, the dropping time of the concentrated sulfuric acid is 0 to 1 hour, and the heat preservation reaction time is 0.5 to 3 hours.
4. The method for synthesizing cardanol-modified dicyclopentadiene phenol resin by using a bisphenol method according to claim 2, wherein in step (2), the temperature of product A is raised to 120-150 ℃, phenol is added, and the reaction is carried out for 1-4 hours, wherein the mass ratio of product A to phenol is 1: 10-3: 10.
5. The method for synthesizing cardanol modified dicyclopentadiene phenol resin by using a bisphenol method according to claim 2, wherein the mass ratio of the product B in the step (3) to dicyclopentadiene is 1: 1-6: 1, the dripping time of dicyclopentadiene is 0-1 h, the heat preservation temperature is 80-90 ℃, and the heat preservation reaction time is 1-3 h.
6. The method for synthesizing cardanol modified dicyclopentadiene phenol resin by using a bisphenol method according to claim 2, wherein the reheating temperature in step (3) is 100-120 ℃ and the reaction time is 2-5 hours.
7. The method for synthesizing cardanol modified dicyclopentadiene phenol resin by using a bisphenol method according to claim 2, wherein the degree of vacuum of the decompression dephenolization in step (3) is less than-0.09 MPa, the temperature is 180-200 ℃, and the time is 2-3 hours.
8. The cardanol-modified dicyclopentadiene phenol resin synthesized according to claim 1, wherein the free phenol content of the cardanol-modified dicyclopentadiene phenol resin is less than 0.05%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210383316.8A CN114656376A (en) | 2022-04-13 | 2022-04-13 | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210383316.8A CN114656376A (en) | 2022-04-13 | 2022-04-13 | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114656376A true CN114656376A (en) | 2022-06-24 |
Family
ID=82035820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210383316.8A Pending CN114656376A (en) | 2022-04-13 | 2022-04-13 | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656376A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628856A (en) * | 2009-08-19 | 2010-01-20 | 华东理工大学 | Dicyclopentadiene phenol-containing compound preparation method |
| CN103145649A (en) * | 2012-12-21 | 2013-06-12 | 上海美东生物材料有限公司 | Anacardol-phenol epoxy resin and preparation method thereof |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN103420808A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| CN106977426A (en) * | 2017-05-27 | 2017-07-25 | 哈尔滨师范大学 | A kind of anacardol phenylurea and preparation method thereof |
| CN112480896A (en) * | 2020-11-26 | 2021-03-12 | 天津大港油田滨港集团博弘石油化工有限公司 | Cardanol sulfonate surfactant oil displacement agent and preparation method thereof |
| CN113620846A (en) * | 2020-05-08 | 2021-11-09 | 中石化石油工程技术服务有限公司 | Biomass phenolic resin filtrate reducer and preparation method and application thereof |
-
2022
- 2022-04-13 CN CN202210383316.8A patent/CN114656376A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628856A (en) * | 2009-08-19 | 2010-01-20 | 华东理工大学 | Dicyclopentadiene phenol-containing compound preparation method |
| CN103420808A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN103145649A (en) * | 2012-12-21 | 2013-06-12 | 上海美东生物材料有限公司 | Anacardol-phenol epoxy resin and preparation method thereof |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| CN106977426A (en) * | 2017-05-27 | 2017-07-25 | 哈尔滨师范大学 | A kind of anacardol phenylurea and preparation method thereof |
| CN113620846A (en) * | 2020-05-08 | 2021-11-09 | 中石化石油工程技术服务有限公司 | Biomass phenolic resin filtrate reducer and preparation method and application thereof |
| CN112480896A (en) * | 2020-11-26 | 2021-03-12 | 天津大港油田滨港集团博弘石油化工有限公司 | Cardanol sulfonate surfactant oil displacement agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4551508A (en) | Polyglycidyl ethers, process for production thereof, and cured products thereof | |
| CN110128611B (en) | Low-temperature curing bio-based benzoxazine resin and preparation method thereof | |
| CN111825829B (en) | Triazine ring structure-containing bio-based epoxy resin and preparation method thereof | |
| KR0182263B1 (en) | Naphthol-based epoxy resins, intermediates for the same, process for preparing the same and epoxy resin compositions containing the same | |
| CN110643007B (en) | Preparation method of phenolic resin wood toughening adhesive | |
| CN104744694B (en) | A kind of preparation method of benzoxazine colophony | |
| CN113292703B (en) | Phosphorus-free full-bio-based flame-retardant epoxy resin with excellent thermal and mechanical properties and green preparation method thereof | |
| WO2024120239A1 (en) | Cardanol-based bisphenol, preparation method therefor and application thereof | |
| CN114656376A (en) | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method | |
| CN112705253B (en) | Solid acid catalyst for preparing methyl methoxyacetate and preparation method and application thereof | |
| CN109678880B (en) | Tri-functional benzoxazine monomer based on resveratrol and preparation method thereof | |
| CN109503520B (en) | 5-aldehyde resorcinol diglycidyl ether and preparation method thereof | |
| CN114573773B (en) | Method for preparing modified high-ortho-cresol formaldehyde resin by adopting condensation of amines and aldehydes | |
| CN115124672B (en) | O-cresol formaldehyde resin and preparation method and application thereof | |
| CN110872281A (en) | Tertiary phenol-furfuryl amine type benzoxazine monomer, cured resin and preparation method of copolymer resin of cured resin | |
| CN103467682B (en) | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method | |
| CN115716779A (en) | Cardanol-based bisphenol as well as preparation method and application thereof | |
| JPH03717A (en) | New epoxy compound and preparation thereof | |
| CN116102942A (en) | Anticorrosive high-temperature-resistant waterborne polyurethane coating and preparation method thereof | |
| CN114478427A (en) | High-performance thermosetting resin curing agent/diluent and preparation method thereof | |
| CN111072884B (en) | Preparation method of palmitoyl hexadecanediol modified phenolic resin | |
| CN114249895A (en) | Long-chain hydroxyl-free sulfone ether epoxy resin and preparation method thereof | |
| CN111087562A (en) | Preparation method of blending modified phenolic resin | |
| US3032533A (en) | Process for producing phenol-modified coumarone-indene type resins | |
| CN110734546B (en) | Self-repairing wear-resistant material and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220624 |