CN116535810A - Phenolic resin for producing environment-friendly paper-based copper-clad plate and preparation method thereof - Google Patents
Phenolic resin for producing environment-friendly paper-based copper-clad plate and preparation method thereof Download PDFInfo
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- CN116535810A CN116535810A CN202310390815.4A CN202310390815A CN116535810A CN 116535810 A CN116535810 A CN 116535810A CN 202310390815 A CN202310390815 A CN 202310390815A CN 116535810 A CN116535810 A CN 116535810A
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- phenolic resin
- based copper
- sodium alginate
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- nitrile rubber
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 135
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 127
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 42
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 39
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 35
- 239000000661 sodium alginate Substances 0.000 claims abstract description 35
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 35
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229920001744 Polyaldehyde Polymers 0.000 claims description 50
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 150000002989 phenols Chemical class 0.000 claims description 17
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 16
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 13
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000012745 toughening agent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 231100001231 less toxic Toxicity 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 19
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- -1 halogen flame retardant modified phenolic resin Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- 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
- C08G8/28—Chemically modified polycondensates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to the technical field of phenolic resin, in particular to phenolic resin for producing an environment-friendly paper-based copper-clad plate and a preparation method thereof. Firstly, sodium periodate is used for oxidizing sodium alginate to generate oxidized sodium alginate with aldehyde groups, and then the oxidized sodium alginate is used for replacing part of formaldehyde to react to generate phenolic resin. Because the sodium alginate has good flame retardance, and the waste can enter the nature through biological decomposition, the preparation process is less toxic than the traditional phenolic resin, is more environment-friendly, and the prepared phenolic resin has good flame retardance. A toughening agent nano carboxyl-terminated nitrile rubber is introduced into the phenolic resin, so that the phenolic resin is further improved under the condition of high brittleness of the traditional phenolic resin.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to phenolic resin for producing an environment-friendly paper-based copper-clad plate and a preparation method thereof.
Background
The paper-based copper-clad plate is a plate which is formed by impregnating fiber paper with resin solution, coating copper foil after drying processing and pressing at high temperature and high pressure, is often applied to a printed circuit board, and can be seen everywhere in daily life, such as mobile phones, computers, televisions and the like which are used daily. Safety and reliability are important criteria for products during production and use. Phenolic resin is one of the resins and is often used as an adhesive in paper-based copper clad laminates. As the copper-clad plate adhesive, phenolic resin has the characteristics of high adhesive strength, good heat resistance, excellent electrical insulation and the like, but traditional phenolic resin has poor flame retardance, generally flame retardant is added to improve the flame retardance, and common flame retardants comprise halogen-containing compounds such as tetrabromobisphenol A, high-bromine epoxy resin and the like, so that toxic cancerogenic substances are generated, the harm is brought to human bodies and the environment, and the traditional phenolic resin has large brittleness and limits the application to a certain extent. Therefore, there is a need for improvement in the above-mentioned problems.
Disclosure of Invention
The invention aims to provide phenolic resin for producing an environment-friendly paper-based copper-clad plate and a preparation method thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
the raw materials of the phenolic resin comprise phenolic resin prepolymer and nano carboxyl-terminated nitrile rubber; the raw materials of the phenolic resin prepolymer comprise the following materials: 95 to 105 parts of phenolic compound, 9 to 17 parts of liquid formaldehyde, 45 to 50 parts of polyaldehyde derivative and 4 to 6 parts of glycerin.
Further, the mass ratio of the phenolic resin prepolymer to the nanometer carboxyl-terminated nitrile rubber is 10 (2-3.5).
Further, the polyaldehyde derivative is oxidized sodium alginate; the particle size of the nano carboxyl-terminated nitrile rubber is 50-150 nm.
Further, the oxidized sodium alginate is obtained by oxidizing sodium alginate with potassium periodate.
Further, the preparation of the phenolic resin comprises the following steps:
s1, preparing a polyaldehyde derivative:
dispersing sodium alginate in absolute ethyl alcohol to obtain suspension A; dissolving sodium periodate in water to obtain a solution B; adding the solution B into the suspension A, stirring for oxidation reaction, adding glycol for terminating reaction, pouring the obtained mixture into absolute ethyl alcohol, vigorously stirring, precipitating, filtering, removing impurities, and drying to obtain polyaldehyde derivatives;
s2, preparing a phenolic resin prepolymer:
adding a phenolic compound, a polyaldehyde derivative, liquid formaldehyde, glycerol and an alkaline catalyst into a reaction kettle, and stirring and reacting for 4-6 hours to obtain a phenolic resin prepolymer;
s3, preparing phenolic resin:
and adding nano carboxyl-terminated nitrile rubber into the prepared phenolic resin prepolymer, and uniformly mixing the nano carboxyl-terminated nitrile rubber to prepare the phenolic resin.
Further, in the step S1, in the oxidation reaction process, the mass ratio of sodium periodate to sodium alginate is (3.78-5.40): 1.
further, in step S1, the oxidation reaction process is as follows: in dark condition, the oxidation temperature is 15-25 ℃ and the oxidation time is 5-8 hours.
Further, in step S2, the phenolic compound includes one or more of phenol, hydroquinone, catechol, resorcinol.
Further, the phenolic resin is applied to an environment-friendly paper-based copper-clad plate.
In the invention, in order to enhance the flame retardance and toughness of the phenolic resin, sodium alginate is firstly used as a matrix to prepare the polyaldehyde derivative to replace part of liquid formaldehyde, the phenolic resin prepolymer is prepared, and then the nanometer carboxyl-terminated nitrile rubber and the polyaldehyde derivative are introduced to generate a synergistic effect, so that the toughness of the phenolic resin is obviously enhanced. As the sodium alginate is a natural polysaccharide and the material components are safer, compared with the traditional halogen flame retardant modified phenolic resin, the invention improves the flame retardance of the phenolic resin, and the prepared phenolic resin has less harm to the environment and human body and certain environmental protection.
It should be emphasized that the amount of the nano carboxyl terminated nitrile rubber is not too much, and when too much is added, the nano particles are separated from the phenolic resin prepolymer due to the aggregation property of the nano particles, so that the mechanical property of the phenolic resin product is reduced, and therefore, in the scheme, the polyaldehyde derivative is embedded into the main chain of the phenolic resin, the toughening property is improved through chemical crosslinking, and the physical toughening of the nano carboxyl terminated nitrile rubber generates a synergistic effect, so that the toughness of the phenolic resin is greatly enhanced.
In order to reduce the toxic influence of phenolic resin on human body and environment and improve the flame retardance of the phenolic resin, sodium periodate is firstly used for oxidizing sodium alginate to generate oxidized sodium alginate with aldehyde groups, and then the oxidized sodium alginate is used for replacing part of formaldehyde to react to generate the phenolic resin prepolymer. The sodium alginate is extracted from natural environment-friendly substances, and has good flame retardance, and waste can enter the nature through biological decomposition, so that the preparation process of the phenolic resin prepolymer is more environment-friendly compared with the traditional phenolic resin preparation process, and the finally prepared phenolic resin has good flame retardance.
The invention not only enhances the flame retardant property of the phenolic resin, but also further improves the problem of high brittleness of the traditional phenolic resin. The specific method is that a toughening agent nano carboxyl-terminated nitrile rubber is added into the prepared phenolic resin. The compatibility of the general carboxyl-terminated nitrile rubber and the phenolic resin is poor, so that the two phases have no good bonding strength, the stress and the strain cannot be well transferred between the two phases, and the performance of the blending system is relatively poor. The average particle diameter of the nanometer carboxyl-terminated nitrile rubber is 50-150 nm, the specific surface area is large, the surface energy is high, the interface area between the elastomer and the prepolymer is increased, and therefore the compatibility of two phases is improved; on the other hand, a large number of polar functional groups exist on the surface of the rubber, and can interact with the polar groups on the phenolic resin to generate strong intermolecular acting force, so that the compatibility of two phases is further improved.
Detailed Description
The following description of the embodiments of the present invention will be made in detail, but clearly understood to be a few, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material sources are as follows: sodium periodate (CAS: 7790-28-5), sodium alginate (CAS: 9005-38-3, molecular weight 198.11), nanometer carboxyl terminated nitrile rubber (Beijing chemical institute of petrochemical China), and paraformaldehyde (CAS: 30525-89-4).
In the following examples, liquid formaldehyde was a 36% by mass aqueous solution.
Example 1
A phenolic resin for producing an environment-friendly paper-based copper-clad plate and a preparation method thereof comprise the following steps:
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; 4.32g of sodium periodate is dissolved in 50mL of water to obtain a solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Example 2
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; 4.32g of sodium periodate is dissolved in 50mL of water to obtain a solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
100.0g of a phenolic compound, 45.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerol and 1.2g of an alkaline catalyst N, N-dimethylethanolamine are put into a reaction kettle and stirred to react for 3.5 hours to prepare a phenolic resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Example 3
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; 4.32g of sodium periodate is dissolved in 50mL of water to obtain a solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
100.0g of a phenolic compound, 50.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerol and 1.2g of an alkaline catalyst N, N-dimethylethanolamine are put into a reaction kettle and stirred to react for 3.5 hours to prepare a phenolic resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Example 4
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; 4.32g of sodium periodate is dissolved in 50mL of water to obtain a solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Example 5
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; 4.32g of sodium periodate is dissolved in 50mL of water to obtain a solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:3.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Comparative example 1: the other steps are the same as in example 1, except that the polyaldehyde derivative is not introduced
(1) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 61.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(2) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Comparative example 2: the remainder was the same as in example 1 without introducing nano carboxyl terminated nitrile rubber
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; sodium periodate (molar ratio of sodium periodate to sodium alginate monomer unit is 0.8:1) is dissolved in 50mL of water to obtain solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
Comparative example 3: the same procedure as in example 1 was repeated except that paraformaldehyde was used in place of the polyaldehyde derivative
(1) Preparation of phenolic resin prepolymer
100.0g of phenolic compound, 48.0g of paraformaldehyde, 13.0g of liquid formaldehyde, 5.0g of glycerol and 1.2g of alkaline catalyst N, N-dimethylethanolamine are put into a reaction kettle and stirred for reaction for 3.5 hours to prepare phenolic resin prepolymer.
(2) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:2.5 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Comparative example 4: the procedure of example 1 is followed without the introduction of polyaldehyde derivatives and nano carboxyl terminated nitrile rubber
To the reaction vessel, 100.0g of a phenolic compound, 61.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
Comparative example 5: the mass ratio of the polyaldehyde derivative to the nano carboxyl terminated nitrile rubber was changed, and the rest was the same as in example 1
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; sodium periodate (molar ratio of sodium periodate to sodium alginate monomer unit is 0.8:1) is dissolved in 50mL of water to obtain solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:1 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Comparative example 6: the mass ratio of the polyaldehyde derivative to the nano carboxyl terminated nitrile rubber was changed, and the rest was the same as in example 1
(1) Preparation of polyaldehyde derivatives
10.0g of sodium alginate is dispersed in 50mL of absolute ethyl alcohol to obtain suspension A; sodium periodate (molar ratio of sodium periodate to sodium alginate monomer unit is 0.8:1) is dissolved in 50mL of water to obtain solution B; adding the solution B into the suspension A, reacting for 6 hours under the dark condition, adding 1.24g of ethylene glycol to terminate the reaction, pouring the obtained mixture into 500mL of absolute ethyl alcohol, vigorously stirring, separating out precipitate, filtering, removing impurities, and drying to obtain the polyaldehyde derivative.
(2) Preparation of phenolic resin prepolymer
To the reaction vessel, 100.0g of a phenolic compound, 48.0g of a polyaldehyde derivative, 13.0g of liquid formaldehyde, 5.0g of glycerin and 1.2g of an alkaline catalyst N, N-dimethylethanolamine were charged, and the reaction was stirred for 3.5 hours to obtain a phenol resin prepolymer.
(3) Preparation of phenolic resins
Mixing the phenolic resin prepolymer with the mass ratio of 10:4 with the nanometer carboxyl-terminated nitrile rubber, and uniformly stirring by a high-speed stirrer to obtain the phenolic resin.
Experiment
The phenolic resins obtained in examples 1 to 5 and comparative examples 1 to 6 were respectively impregnated with a weight of 135g/m 2 And (3) drying to obtain prepregs with the resin content of 40-45%, superposing 8 prepregs, coating a copper foil with the thickness of 0.25 mu m on one surface, and pressing for 90 minutes under the conditions of unit pressure of 30MP a and temperature of 160 ℃ to obtain the paper-based copper-clad plate with the thickness of 1.8 mm.
The impact resistance of the phenolic resin-pressed copper-clad laminates obtained in examples 1 to 5 and comparative examples 1 to 6 was measured according to the standard GB1043-79, the flexural strength of the phenolic resin-pressed copper-clad laminates obtained in examples 1 to 5 and comparative examples 1 to 6 was measured according to the standard GB9641-88, and the oxygen index of the phenolic resin-pressed copper-clad laminates obtained in examples 1 to 5 and comparative examples 1 to 6 was measured according to the standard GB/T2406. The detection results are shown in the following table:
| impact resistancedegree/(KJ/m) 2 ) | Flexural Strength/MPa | Oxygen index/% | |
| Example 1 | 7.04 | 31.32 | 30 |
| Example 2 | 6.85 | 30.87 | 29 |
| Example 3 | 6.75 | 30.21 | 29 |
| Example 4 | 6.37 | 29.59 | 28 |
| Example 5 | 6.54 | 30.64 | 29 |
| Comparative example 1 | 5.46 | 28.32 | 24 |
| Comparative example 2 | 5.02 | 24.63 | 28 |
| Comparative example 3 | 5.35 | 25.13 | 23 |
| Comparative example 4 | 3.97 | 23.92 | 23 |
| Comparative example 5 | 5.33 | 25.74 | 28 |
| Comparative example 6 | 5.62 | 26.34 | 29 |
From the data in the above table, the following conclusions can be clearly drawn:
1. compared with comparative examples 1 and 4, the paper-based copper-clad laminate prepared from the phenolic resin obtained in examples 1 to 3 has a higher oxygen index; this fully demonstrates that the addition of the polyaldehyde derivative of the present invention achieves the aim of improving the flame retardancy of phenolic resins.
2. Compared with comparative examples 2 and 4, the paper-based copper-clad plate prepared from the phenolic resin obtained in examples 1-3 has higher impact resistance and bending resistance; the addition of the nano carboxyl terminated nitrile rubber can obviously enhance the toughness of the phenolic resin.
3. Compared with comparative example 4, the paper-based copper-clad plate prepared by the phenolic resin obtained in comparative example 2 has improved oxygen index, and improved impact strength and bending strength, which shows that the addition of the polyaldehyde derivative not only improves the flame retardant property of the phenolic resin, but also has a certain toughening effect on the phenolic resin; meanwhile, compared with comparative example 2, the paper-based copper-clad plate prepared from the phenolic resin obtained in examples 1-3 has improved impact resistance and bending strength, and compared with comparative example 1, the method shows that the toughening effect of the polyaldehyde derivative oxidized sodium alginate and the nanometer carboxyl-terminated nitrile rubber is stronger than that of the nanometer carboxyl-terminated nitrile rubber which is independently introduced, and the performance test data of comparative examples 2 and 4 are compared, so that the introduced polyaldehyde derivative oxidized sodium alginate and the nanometer carboxyl-terminated nitrile rubber have synergistic toughening effect.
4. The significantly higher oxygen index of the phenolic resins obtained in examples 1-3 compared to comparative example 3 demonstrates that substitution of a polyaldehyde derivative for a portion of formaldehyde in the preparation of the phenolic resin can significantly improve the flame retardant properties of the phenolic resin, which is a point of distinction between polyaldehyde derivatives prepared by oxidation of sodium alginate with sodium periodate and paraformaldehyde.
5. Compared with comparative examples 5-6, the oxygen index, impact resistance and bending strength of the paper-based copper-clad laminate prepared by the phenolic resin in examples 1-3 are all higher, which indicates that the mass ratio of the polyaldehyde derivative to the nano carboxyl-terminated nitrile rubber in the preparation process of the phenolic resin is in a better range, when the addition amount of the nano carboxyl-terminated nitrile rubber is smaller, the nano carboxyl-terminated nitrile rubber still has good compatibility with phenolic resin prepolymer in a system, more nano carboxyl-terminated nitrile rubber particles can be accommodated, the toughening effect is enhanced along with the gradual increase of the addition amount, but when the addition amount of the nano carboxyl-terminated nitrile rubber is too large, the nano carboxyl-terminated nitrile rubber can be separated from the phenolic resin prepolymer due to the aggregation of the nano particles, so that the mechanical property of a phenolic resin product is reduced, and therefore, in the scheme, the toughening performance is improved by embedding the polyaldehyde derivative into a phenolic resin main chain, the physical toughening effect of the nano carboxyl-terminated nitrile rubber is generated, and the toughness of the phenolic resin is greatly enhanced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A phenolic resin for producing environment-friendly paper-based copper-clad plates is characterized in that: the raw materials of the phenolic resin comprise phenolic resin prepolymer and nano carboxyl-terminated nitrile rubber; the raw materials of the phenolic resin prepolymer comprise the following materials: 95 to 105 parts of phenolic compound, 9 to 17 parts of liquid formaldehyde, 45 to 50 parts of polyaldehyde derivative and 4 to 6 parts of glycerin.
2. The phenolic resin for producing an environmentally friendly paper-based copper clad laminate according to claim 1, wherein: the mass ratio of the phenolic resin prepolymer to the nanometer carboxyl-terminated nitrile rubber is 10 (2-3.5).
3. The phenolic resin for producing an environmentally friendly paper-based copper clad laminate according to claim 1, wherein: the polyaldehyde derivative is oxidized sodium alginate; the particle size of the nano carboxyl-terminated nitrile rubber is 50-150 nm.
4. A phenolic resin for producing an environmentally friendly paper-based copper clad laminate as claimed in claim 3, wherein: the oxidized sodium alginate is obtained by oxidizing sodium alginate with potassium periodate.
5. A preparation method of phenolic resin for producing an environment-friendly paper-based copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a polyaldehyde derivative:
dispersing sodium alginate in absolute ethyl alcohol to obtain suspension A; dissolving sodium periodate in water to obtain a solution B; adding the solution B into the suspension A, stirring for oxidation reaction, adding glycol for terminating reaction, pouring the obtained mixture into absolute ethyl alcohol, vigorously stirring, precipitating, filtering, removing impurities, and drying to obtain polyaldehyde derivatives;
s2, preparing a phenolic resin prepolymer:
adding a phenolic compound, a polyaldehyde derivative, liquid formaldehyde, glycerol and an alkaline catalyst into a reaction kettle, and stirring and reacting for 4-6 hours to obtain a phenolic resin prepolymer;
s3, preparing phenolic resin:
and adding nano carboxyl-terminated nitrile rubber into the prepared phenolic resin prepolymer, and uniformly mixing the nano carboxyl-terminated nitrile rubber to prepare the phenolic resin.
6. The preparation method of the phenolic resin for producing the environment-friendly paper-based copper-clad plate according to claim 5, wherein in the step S1, the mass ratio of sodium periodate to sodium alginate is (3.78-5.40): 1.
7. the method for producing a phenolic resin for producing an environmentally friendly paper-based copper-clad plate according to claim 5, wherein in step S1, the oxidation reaction process is as follows: in dark condition, the oxidation temperature is 15-25 ℃ and the oxidation time is 5-8 hours.
8. The method for preparing the phenolic resin for producing the environment-friendly paper-based copper-clad plate according to claim 5, which is characterized in that: in step S2, the phenolic compound includes one or more of phenol, hydroquinone, catechol, and resorcinol.
9. Use of a phenolic resin according to any one of claims 1 to 8, characterized in that: the phenolic resin is applied to an environment-friendly paper-based copper-clad plate.
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| US20110060105A1 (en) * | 2007-12-20 | 2011-03-10 | Nanoresins Ag | Modified phenol resins |
| CN106476390A (en) * | 2017-01-03 | 2017-03-08 | 山东金宝科创股份有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN106854264A (en) * | 2016-12-02 | 2017-06-16 | 江南大学 | A kind of rice husk sill quality modified phenolic resin adhesive preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110060105A1 (en) * | 2007-12-20 | 2011-03-10 | Nanoresins Ag | Modified phenol resins |
| CN106854264A (en) * | 2016-12-02 | 2017-06-16 | 江南大学 | A kind of rice husk sill quality modified phenolic resin adhesive preparation method |
| CN106476390A (en) * | 2017-01-03 | 2017-03-08 | 山东金宝科创股份有限公司 | A kind of preparation method of paper-based copper-coated board |
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