CN111284088A - Preparation method of heat-resistant modified phenolic paper-based copper-clad laminate - Google Patents
Preparation method of heat-resistant modified phenolic paper-based copper-clad laminate Download PDFInfo
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
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- C09J161/14—Modified phenol-aldehyde condensates
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/028—Paper layer
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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Abstract
The invention relates to a preparation method of a heat-resistant modified phenolic paper-based copper-clad laminate, which comprises the following steps of (I) preparing tung oil anhydride resin, wherein the raw materials comprise the following components in parts by mass: 800 portions of tung oil, 400 portions of maleic anhydride and 500 portions of methanol; preparing heat-resistant modified phenolic resin, and taking indole acrylic acid or salt thereof as a modifier; thirdly, the mixture of tung oil anhydride resin and bisphenol A modified phenolic resin can be used as the adhesive of the paper-based copper-clad laminate; and (IV) impregnating the insulating paper with the binder, drying, cutting to prepare a phenolic paper-based prepreg, and then covering a copper foil for compression molding. The application designs the heat-resistant modified phenolic resin to improve the heat resistance, and crosslinking and curing are carried out by using tung oil anhydride to improve the toughness.
Description
Technical Field
The invention relates to a binder for a copper-clad laminate, in particular to a binder for a paper-based copper-clad laminate, and specifically belongs to a modified phenolic resin binder.
Background
The copper-clad laminate is a plate-shaped material formed by hot pressing reinforcing material soaked with resin and one or two sides coated with copper foil, wherein the resin is used as a binder and is crosslinked and cured in the hot pressing process. The copper-clad plate is a base material of the PCB, and different printed boards are manufactured into different printed circuits by processing, etching, drilling, copper plating and other processes on the copper-clad plate.
The phenolic paper-based copper-clad plate still occupies important market share, the compatible binder is preferably phenolic resin, the phenolic resin is a copolymer of phenol and formaldehyde, and has good heat resistance and chemical resistance, but high modulus, and the defects of high brittleness, easy generation of interface stress crack, poor toughness, low impact strength and the like. Modification of the phenolic resin is therefore an essential means for the phenolic resin to act as a binder. Phenolic resins are used as binders with general emphasis on toughness and heat resistance modification.
The toughening modification of the phenolic resin can be realized by adding an external toughening agent into a system, such as thermoplastic resins of natural rubber, nitrile rubber, styrene butadiene rubber, polybutadiene and the like; or the toughness of the phenolic resin is improved by modifying and introducing an internal toughening agent into a molecular chain, such as introducing a long hydrocarbon chain between phenyl groups of phenol or etherifying phenolic hydroxyl groups. In the prior art, the modified phenolic resin obtained by modifying phenolic resin by adopting cashew nut oil and tung oil belongs to internal toughening reaction. Publication No. CN103087467B discloses a preparation method of a tung oil modified phenolic resin composition: adding 15 to 25 percent of phenol and 5 to 15 percent of tung oil into a reaction kettle, stirring, and adding 0.1 to 1 percent of methanol solution of p-toluenesulfonic acid when the kettle temperature reaches 45 to 55 ℃; heating to 60-100 deg.c, reaction at the temperature for 90-150 min, adding 0.1-1% concentration water solution of triethanolamine and cooling to 50-70 deg.c; adding 10 to 50 percent of formaldehyde, adding 0.1 to 0.5 percent of triethylamine and 0.5 to 5 percent of ammonia water, automatically heating the kettle to 60 to 90 ℃, keeping the reaction at a constant temperature, introducing cooling water for cooling and starting vacuum dehydration when the gelling time is determined to be 100 to 200 seconds; and when the temperature is reduced to be below 50-80 ℃, closing a cooling water valve and heating to ensure dehydration, raising the temperature back to be above 50-80 ℃, cooling after the resin is transparent, adding 1-10% of a toughening agent and 10-50% of methanol, uniformly stirring and discharging. The tung oil modified phenolic resin composition obtained according to the preparation method and the insulating paperboard prepared by the tung oil modified phenolic resin composition can provide an insulating structural member which is prepared by tung oil modified phenolic resin and has excellent insulating property and good adhesive force with other insulating layers.
Among the heat resistance modifications of phenolic resins, boron modification is an important research subject, and such modification can significantly improve heat resistance and high temperature resistance, while mechanical properties such as impact strength can also be improved. The patent document with the publication number 106317354B discloses a preparation method of high-temperature resistant phenolic resin, which comprises the following raw materials: 1000 parts of phenol; 687.2 parts of formaldehyde; 6 parts of oxalic acid; 4.7 parts of aniline; 400 portions of saturated monohydric alcohol and 750 portions of saturated monohydric alcohol; 40 parts of boric acid; 1-2.03 parts of one of magnesium oxide, calcium oxide or zinc oxide. Because the bond energy of B-O is higher than that of C-C, the cured product contains a three-dimensional cross-linked network structure of boron, and therefore, the heat resistance and the ablation resistance of the cured product are greatly higher than those of common phenolic resin.
In addition, the aromatic hydrocarbon modified phenolic resin can also play a role in toughening and stabilizing, the aromatic hydrocarbon can divide and surround the phenolic structure, the water resistance and the rigidity of the resin are improved, the whole polymer chain is stabilized, and the purpose of improving the heat resistance is achieved. Patent document No. 105585679B discloses a method for producing a cashew nut shell oil-modified resorcinol aldehyde resin, in which an aldehyde compound is added to a mixture containing resorcinol or alkylated resorcinol and a prepolymer (R0) of cashew nut shell oil-modified resorcinol to perform polycondensation reaction, thereby producing a cashew nut shell oil-modified resorcinol aldehyde resin of formula (I). The cashew nut shell oil modified resorcinol aldehyde resin disclosed by the invention can be used as an adhesion promoter composition and is widely applied to rubber products.
With the gradual miniaturization and miniaturization development of electronic and electrical equipment, the demand of the market on thin PCB boards is increased, the smaller the thickness of the PCB board is, the higher the modification difficulty of toughness and heat resistance is, and the traditional phenolic resin can not ensure that the delivery performance of the thin copper-clad laminated board meets the market requirement.
Disclosure of Invention
Compared with the traditional tung oil modified phenolic resin, the phenolic resin binder developed by the application has the design idea that tung oil is converted into tung oil anhydride resin and then is mixed with the heat-resistant modified phenolic resin, and the prepared binder is applied to the preparation of the paper-based copper-clad laminate and can obviously improve the toughness and the temperature resistance.
Compared with other thermosetting resin materials, the phenolic resin has higher curing temperature, and the physical property and chemical resistance of the cured material are basically equivalent to the level of unsaturated polyester, but compared with polyester and epoxy resin, the phenolic resin has brittle and hard texture and higher shrinkage rate. The tung oil modified phenolic resin belongs to internal toughening modification, the polymerization degree of the phenolic resin is obviously reduced, and hydrocarbon chains and ester groups are substituted, so that the electrical resistance (insulating property), toughness and viscosity of the phenolic resin can be obviously improved. The tung oil mainly comprises tung oil triglyceride, has three long chains, belongs to space macromolecules, and is influenced by the structure, so that the attraction among molecular chains of the tung oil modified phenolic resin is reduced, and the crosslinking density is reduced.
The technical scheme adopted by the invention for solving the problems is as follows: a preparation method of a heat-resistant modified phenolic paper-based copper-clad laminate is characterized by comprising the following steps: comprises the following steps
(I) preparation of tung oil anhydride resin
The raw materials of the tung oil anhydride resin are proportioned by mass as follows
800 portions of tung oil and 1000 portions of,
200 portions of maleic anhydride and 400 portions of maleic anhydride,
300 portions of methanol and 500 portions of methanol,
sequentially adding tung oil and maleic anhydride into a reaction kettle, uniformly stirring, sealing the reaction kettle, heating the reaction kettle to 60 +/-5 ℃, stopping heating, starting the reaction of the tung oil and the maleic anhydride, releasing heat in the reaction to raise the temperature in the reaction kettle, opening interlayer cooling water of the reaction kettle when the temperature is raised to be close to 140 ℃ to maintain the temperature in the reaction kettle at 140-155 ℃, reacting for 40-60min at the temperature, then sampling and detecting, dripping dimethylaniline, observing the color of the reactant, continuing the reaction in the reaction kettle if the reactant is red, till the color of the sample does not change after the dimethylaniline is dripped, reacting for 10-20min, starting cooling water to cool the reaction kettle, adding methanol for dilution when the temperature of the reaction kettle is cooled to be close to 80 ℃, and stopping cooling when the temperature is cooled to be close to 40 ℃;
(II) preparing the heat-resistant modified phenolic resin
The heat-resistant modified phenolic resin comprises the following raw materials in parts by mass
1800-2200 parts of indoleacrylic acid or salt thereof
1800 portions of 1100 portions of phenol
Oxalic acid 5-8 parts
1000 portions of formaldehyde
20-25 parts of triethylamine
10-15 parts of ammonia water
3000 portions of methanol and 5000 portions
20-60 parts of titanium dioxide
Preparing a reaction kettle, sequentially adding indole acrylic acid or salts thereof, phenol and oxalic acid into the reaction kettle according to the amount, taking the oxalic acid as a catalyst, stirring and heating to 40-50 ℃, stopping heating, reacting for 20-40min, then continuously heating to 80-90 ℃, reacting for more than 120min, then cooling the reaction kettle to 40-50 ℃, adding formaldehyde, triethylamine and ammonia water, carrying out a secondary reaction at the reaction temperature of 90-130 ℃, reacting for more than 150 min, dehydrating after the reaction is finished, carrying out vacuum dehydration, evaporating part of unreacted indole acrylic acid or salts thereof, oxalic acid and ammonia water along with water in the dehydration process, adding methanol for dilution after the dehydration is finished, then adding titanium dioxide according to the formula amount, uniformly mixing to prepare white heat-resistant modified phenolic resin, and keeping in a dark place;
(III) preparing a modified phenolic resin mixed solution
Mixing the tung oil anhydride resin prepared in the step (I) and the heat-resistant modified phenolic resin prepared in the step (II) according to the weight ratio of 1 (3-4), stirring for 30min to obtain a binder of the paper-based copper-clad laminate, and storing the binder in a light-tight sealed manner;
(IV) preparation of paper-based copper-clad laminate
And (3) impregnating the insulating paper with the binder prepared in the step (III) for one or more times, drying, cutting to prepare a phenolic paper-based prepreg, and covering with copper foil for press forming.
Preferably, in the step (one), the raw materials of the tung oil anhydride resin are mixed according to the following mass portion
800 portions of tung oil and 900 portions of,
200 portions and 300 portions of maleic anhydride,
400 portions of methanol and 500 portions of methanol.
Further, in the step (one), the raw materials of the tung oil anhydride resin are mixed according to the following mass portion
800 parts of tung oil,
280 portions and 300 portions of maleic anhydride,
400 portions of methanol and 420 portions.
Preferably, in the step (two), the salt of indoleacrylic acid comprises sodium indoleacrylate, potassium indoleacrylate, iron indoleacrylate and titanium indoleacrylate.
Preferably, in step (two), the oxalic acid is in the form of a 2 wt% to 10 wt% aqueous solution.
Preferably, in step (two), the aqueous solution of ammonia has a concentration of 0.5 to 6% by weight.
Preferably, in the step (two), the mass parts of the raw materials of the heat-resistant modified phenolic resin are as follows
1800-2000 parts of indoleacrylic acid or its salt
1200 parts of phenol 1100-
5-6 parts of oxalic acid
1000 portions of formaldehyde
20-22 parts of triethylamine
10 portions of ammonia water
3000 portions of methanol and 4200 portions
30-40 parts of titanium dioxide.
Compared with the prior art, the invention has the advantages that:
(1) in the invention, conjugated olefin structures on three unsaturated ester chains of tung oil and maleic anhydride are synthesized into tung oil anhydride, so that six-membered ring anhydride structures are formed on the three ester chains, and during crosslinking, the rings are opened, and one six-membered ring anhydride structure forms two active sites, thereby improving the crosslinking density of phenolic resin of tung oil anhydride, improving the modulus, toughening and reinforcing.
(2) In the heat-resistant modified phenolic resin, indole acrylic acid and phenol react to generate indole phenyl acrylate under the condition of strong acid (oxalic acid is used as a catalyst in the application), indole and olefin groups are introduced on a phenol nucleus, and indole has six-membered phenyl and five-membered pyrrole, so that the stability of the phenolic resin can be obviously improved, the storage time is prolonged, the heat resistance is improved, and the modification effect of the phenolic resin can refer to the modification effect of aromatic hydrocarbon on the phenolic resin.
(3) Indole acrylic acid or salt thereof is used as a modifier of the phenolic resin, a five-membered heterocyclic ring structure contains an imine structure and a relatively stable unsaturated bond, and an acrylic acid side chain contains an unsaturated bond which is just conjugated with the imine and the unsaturated bond of the five-membered heterocyclic ring, so that on one hand, the alkalescence of the imine structure can be reduced, on the other hand, the conjugated structure can be subjected to electrophilic substitution under an acidic condition and is subjected to para-position addition with phenolic hydroxyl, and the reaction principle is similar to that of the tung oil modified phenolic resin.
(4) The reaction of indole acrylic acid with phenol described in the above (2) and (3) is different reaction mechanisms, one is esterification reaction and one is addition reaction, theoretically, one molecule of indole acrylic acid can react with 1 to 2 phenols as long as the reaction conditions and the ratio are appropriate.
(5) The molecular structure of the heat-resistant modified phenolic resin prepared by the invention contains phenyl, pentacyclic heterocycle, ester group and phenolic hydroxyl, and the heat resistance and rigidity are obviously improved. Mixing tung oil anhydride resin and heat-resistant modified phenolic resin, and crosslinking the open ring of six-membered ring on the molecular chain of tung oil anhydride resin with the active site of the heat-resistant modified phenolic resin. High crosslinking density, high mechanical strength and high electric resistance.
Detailed Description
The present invention is described in further detail below with reference to examples, which are illustrative and are not to be construed as limiting the present invention.
Example 1
The preparation method of the heat-resistant modified phenolic paper-based copper-clad laminate comprises the following steps
(I) preparation of tung oil anhydride resin
The raw materials of the tung oil anhydride resin are proportioned by mass, each part corresponds to 1kg
800 parts of tung oil,
280 parts of maleic anhydride and 280 parts of maleic anhydride,
420 parts of methanol, namely methanol, and the like,
sequentially adding tung oil and maleic anhydride after metering, uniformly stirring the tung oil and the maleic anhydride, sealing the reaction kettle, heating the reaction kettle, raising the temperature to 58-60 ℃, stopping heating, starting reaction of the tung oil and the maleic anhydride at the moment, carrying out diene addition cyclization reaction on conjugated double bonds in molecular structures of the maleic anhydride and the tung oil to generate a stable six-membered ring structure, releasing heat to raise the temperature in the reaction kettle, opening interlayer cooling water of the reaction kettle when the temperature is raised to be close to 140 ℃ to maintain the temperature in the reaction kettle at 140-150 ℃, reacting for 40min at the temperature, then sampling and detecting, dropwise adding dimethylaniline, observing the color of a reactant, if the reactant is red, indicating that the reaction in the reaction kettle is not complete, continuing the reaction in the reaction kettle until the color of the sample is not changed after dropwise adding the dimethylaniline, reacting for 10min again, and (3) starting cooling water to cool the reaction kettle, adding methanol for dilution when the temperature of the reaction kettle is cooled to be close to 80 ℃, and closing the cooling water of the reaction kettle when the temperature is cooled to be close to 40 ℃.
(II) preparing the heat-resistant modified phenolic resin
The heat-resistant modified phenolic resin comprises the following raw materials in parts by mass
1800 parts of indoleacrylic acid
1600 parts of phenol
6 parts of 3 weight percent oxalic acid solution
1200 parts of formaldehyde
20-25 parts of triethylamine
10-15 parts of 6 wt% ammonia water
3000 portions of methanol and 5000 portions
30 parts of titanium dioxide
Preparing a reaction kettle, sequentially adding indole acrylic acid, phenol and oxalic acid into the reaction kettle according to the measurement, taking oxalic acid as a catalyst, heating to 50 ℃ while stirring, stopping heating, reacting at a constant temperature for 30min, continuously heating to 80-90 ℃, reacting for 2h, cooling the reaction kettle to 40-50 ℃, adding formaldehyde, triethylamine and ammonia water, performing condensation reaction under an alkaline condition, reacting at the temperature of 110-130 ℃, reacting for 3 h, performing vacuum dehydration after the reaction is finished, evaporating residual indole acrylic acid, oxalic acid and the like along with water in the dehydration process, adding methanol for dilution after the dehydration is finished, adding titanium dioxide according to the formula amount, uniformly mixing to obtain white heat-resistant modified phenolic resin, and storing in a closed and dark place.
(III) preparing a modified phenolic resin mixed solution
And (3) mixing the tung oil anhydride resin prepared in the step (I) and the heat-resistant modified phenolic resin prepared in the step (II) according to the weight ratio of 1:4, stirring for 40min, and then using the mixture as a binder of the paper-based copper-clad laminate, wherein the binder is sealed and stored in a dark place.
(IV) preparation of paper-based copper-clad laminate
And (3) drying and slitting the binder prepared in the step (III) by dipping the wood fiber paper twice to prepare a phenolic paper-based prepreg, pressing the three prepreg layers to form a phenolic paper base, and covering copper foil on one or two surfaces of the phenolic paper base to obtain the copper-clad laminated board.
Example 2
The preparation method of the heat-resistant modified phenolic paper-based copper-clad laminate comprises the following steps
(I) preparation of tung oil anhydride resin
The raw materials of the tung oil anhydride resin are proportioned by mass, each part corresponds to 1kg
900 parts of tung oil,
310 parts of maleic anhydride, and the like,
420 parts of methanol, namely methanol, and the like,
sequentially adding tung oil and maleic anhydride after metering, uniformly stirring the tung oil and the maleic anhydride, sealing the reaction kettle, heating the reaction kettle, raising the temperature to 58-60 ℃, stopping heating, starting reaction of the tung oil and the maleic anhydride at the moment, carrying out diene addition cyclization reaction on conjugated double bonds in molecular structures of the maleic anhydride and the tung oil to generate a stable six-membered ring structure, releasing heat to raise the temperature in the reaction kettle, opening interlayer cooling water of the reaction kettle when the temperature is raised to be close to 140 ℃ to maintain the temperature in the reaction kettle at 140-150 ℃, reacting for 40min at the temperature, then sampling and detecting, dropwise adding dimethylaniline, observing the color of a reactant, if the reactant is red, indicating that the reaction in the reaction kettle is not complete, continuing the reaction in the reaction kettle until the color of the sample is not changed after dropwise adding the dimethylaniline, reacting for 20min again, and (3) starting cooling water to cool the reaction kettle, adding methanol for dilution when the temperature of the reaction kettle is cooled to 70-80 ℃, and closing the cooling water of the reaction kettle when the temperature is cooled to be close to 40 ℃.
(II) preparing the heat-resistant modified phenolic resin
The heat-resistant modified phenolic resin comprises the following raw materials in parts by mass
2000 parts of potassium indolylacrylate
1400 parts of phenol
6 parts of 4 wt% oxalic acid solution
1200 parts of formaldehyde
Triethylamine 24 portions
15 portions of 3 percent ammonia water
4000 parts of methanol
45 parts of titanium dioxide
Preparing a reaction kettle, sequentially adding potassium indole acrylate, phenol and oxalic acid into the reaction kettle according to the amount, taking oxalic acid as a catalyst, stirring and heating to 40 ℃, stopping heating, keeping the temperature for reaction for 30min, then continuously heating to 80-90 ℃, reacting for 2h, then cooling the reaction kettle to 40-50 ℃, adding formaldehyde, triethylamine and ammonia water, adjusting the system to be alkaline, carrying out secondary reaction, reacting for 150 min at the temperature of 100-120 ℃, dehydrating after the reaction is finished, carrying out vacuum dehydration, evaporating part of unreacted potassium indole acrylate, oxalic acid and ammonia water along with water in the dehydration process, adding methanol for dilution after the dehydration is finished, then adding titanium dioxide according to the formula amount, uniformly mixing to prepare the white heat-resistant modified phenolic resin, and keeping out of the sun.
(III) preparing a modified phenolic resin mixed solution
And (3) mixing the tung oil anhydride resin prepared in the step (I) and the heat-resistant modified phenolic resin prepared in the step (II) according to the weight ratio of 1:4, stirring for 30min, and then using the mixture as a binder of the paper-based copper-clad laminate, wherein the binder is sealed and stored in a dark place.
(IV) preparation of paper-based copper-clad laminate
And (3) drying and slitting the binder prepared in the step (III) by dipping the wood fiber paper twice to prepare a phenolic paper-based prepreg, pressing the three prepreg layers to form a phenolic paper base, and covering copper foil on one or two surfaces of the phenolic paper base to obtain the copper-clad laminated board.
Comparative example 1
The preparation method of the tung oil modified phenolic paper-based copper-clad laminate comprises the following steps
Step one, tung oil modified phenolic resin
The raw materials of the tung oil modified phenolic resin are proportioned by mass as follows, each part corresponds to 1kg
500 parts of tung oil, namely 500 parts of tung oil,
700 parts of phenol, namely 700 parts of phenol,
6 parts of p-toluenesulfonic acid aqueous solution (concentration 50 wt%),
a proper amount of triethanolamine is added,
640 parts of formaldehyde, namely formaldehyde, wherein the formaldehyde comprises the following components,
16 parts of ammonia water, namely 16 parts of ammonia water,
700 parts of methanol, namely methanol, and the like,
the tung oil, the phenol and the p-toluenesulfonic acid aqueous solution are measured and then sequentially added into a reaction kettle, the mixture is uniformly stirred, the reaction kettle is sealed and heated, the temperature is raised to 80 ℃, and the first step of reaction is carried out: reacting tung oil and phenol, adding phenol and tung oil molecules, adding a phenol core on three conjugated olefin chains of the tung oil, reacting one tung oil molecule corresponding to 1-6 phenol monomers at 80 ℃ for 120min, and adjusting triethanolamine to be neutral after the reaction is finished; then carrying out a second step of reaction: adding formaldehyde and ammonia water into a reaction kettle, carrying out phenolic aldehyde reaction under an alkaline condition, wherein the product contains water, the reaction temperature is set to be 90-95 ℃, the reaction is carried out for more than 120min, dehydration is carried out after the reaction is finished, then methanol is added for dilution, and the mixture is kept stand for 1 hour to be used as a binder of the paper-based copper-clad laminated board.
Step (II) preparation of paper-based copper-clad laminate
And (2) drying and slitting the binder prepared in the step (I) by dipping the wood fiber paper twice to prepare a phenolic paper-based prepreg, pressing the three prepreg layers to form a phenolic paper base, and covering copper foil on one or two surfaces of the phenolic paper base to obtain the copper-clad laminated board.
Comparative example 2
The heat-resistant modified phenolic resin prepared in the second step of the example 2 is used as the binder of the paper-based phenolic copper-clad laminate.
And (2) drying and slitting the binder prepared in the step (I) by dipping the wood fiber paper twice to prepare a phenolic paper-based prepreg, pressing the three prepreg layers to form a phenolic paper base, and covering copper foil on one or two surfaces of the phenolic paper base to obtain the copper-clad laminated board.
Comparative example 3
The tung oil modified phenolic resin of comparative example 1 and the heat-resistant modified phenolic resin of comparative example 2 were mixed in a ratio of 1:1 to serve as binders for paper-based phenolic copper clad laminates.
And (2) drying and slitting the binder prepared in the step (I) by dipping the wood fiber paper twice to prepare a phenolic paper-based prepreg, pressing the three prepreg layers to form a phenolic paper base, and covering copper foil on one or two surfaces of the phenolic paper base to obtain the copper-clad laminated board.
The results of the main property tests of examples 1 and 2 and comparative examples 1, 2 and 3 are shown in Table 1
TABLE 1
In the surface resistance detection, the conditions of the wet heat treatment are as follows: the temperature is 40-43 deg.C, the humidity is above 95%, the maintaining time is 4 days, and the recovery time is 120 min.
Although preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that modifications and variations of the present invention are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a heat-resistant modified phenolic paper-based copper-clad laminate is characterized by comprising the following steps: comprises the following steps
(I) preparation of tung oil anhydride resin
The raw materials of the tung oil anhydride resin are proportioned by mass as follows
800 portions of tung oil and 1000 portions of,
200 portions of maleic anhydride and 400 portions of maleic anhydride,
300 portions of methanol and 500 portions of methanol,
sequentially adding tung oil and maleic anhydride into a reaction kettle, uniformly stirring, sealing the reaction kettle, heating the reaction kettle to 60 +/-5 ℃, stopping heating, starting the reaction of the tung oil and the maleic anhydride, releasing heat in the reaction to raise the temperature in the reaction kettle, opening interlayer cooling water of the reaction kettle when the temperature is raised to be close to 140 ℃ to maintain the temperature in the reaction kettle at 140-155 ℃, reacting for 40-60min at the temperature, then sampling and detecting, dripping dimethylaniline, observing the color of the reactant, continuing the reaction in the reaction kettle if the reactant is red, till the color of the sample does not change after the dimethylaniline is dripped, reacting for 10-20min, starting cooling water to cool the reaction kettle, adding methanol for dilution when the temperature of the reaction kettle is cooled to be close to 80 ℃, and stopping cooling when the temperature is cooled to be close to 40 ℃;
(II) preparing the heat-resistant modified phenolic resin
The heat-resistant modified phenolic resin comprises the following raw materials in parts by mass
1800-2200 parts of indoleacrylic acid or salt thereof
1800 portions of 1100 portions of phenol
Oxalic acid 5-8 parts
1000 portions of formaldehyde
20-25 parts of triethylamine
10-15 parts of ammonia water
3000 portions of methanol and 5000 portions
20-60 parts of titanium dioxide
Preparing a reaction kettle, sequentially adding indole acrylic acid or salts thereof, phenol and oxalic acid into the reaction kettle according to the amount, taking the oxalic acid as a catalyst, stirring and heating to 40-50 ℃, stopping heating, reacting for 20-40min, then continuously heating to 80-90 ℃, reacting for more than 120min, then cooling the reaction kettle to 40-50 ℃, adding formaldehyde, triethylamine and ammonia water, carrying out a secondary reaction in an alkaline environment, reacting for 180 min at 90-130 ℃, dehydrating after the reaction is finished, carrying out vacuum dehydration, evaporating part of unreacted indole acrylic acid or salts thereof, oxalic acid and ammonia water along with water in the dehydration process, adding methanol for dilution after the dehydration is finished, then adding titanium dioxide according to the formula amount, uniformly mixing to prepare white heat-resistant modified phenolic resin, and storing in a dark place;
(III) preparing a modified phenolic resin mixed solution
Mixing the tung oil anhydride resin prepared in the step (I) and the heat-resistant modified phenolic resin prepared in the step (II) according to the weight ratio of 1 (3-4), stirring for more than 30min to obtain a binder of the paper-based copper-clad laminate, and storing the binder in a light-tight sealing manner;
(IV) preparation of paper-based copper-clad laminate
And (3) impregnating the insulating paper with the binder prepared in the step (III) for one or more times, drying, cutting to prepare a phenolic paper-based prepreg, and covering with copper foil for press forming.
2. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (one), the raw materials of the tung oil anhydride resin are mixed according to the mass part ratio
800 portions of tung oil and 900 portions of,
200 portions and 300 portions of maleic anhydride,
400 portions of methanol and 500 portions of methanol.
3. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (one), the raw materials of the tung oil anhydride resin are mixed according to the mass part ratio
800 parts of tung oil,
280 portions and 300 portions of maleic anhydride,
400 portions of methanol and 420 portions.
4. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (II), the salt of the indoleacrylic acid comprises sodium indoleacrylate, potassium indoleacrylate, iron indoleacrylate and titanium indoleacrylate.
5. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (II), the oxalic acid is 2-10 wt% aqueous solution.
6. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (II), the concentration of the ammonia water is 0.5-6 wt% of the aqueous solution.
7. The method for preparing the heat-resistant modified phenolic paper-based copper-clad laminate according to claim 1, characterized in that: in the step (II), the heat-resistant modified phenolic resin comprises the following raw materials in parts by mass
1800-2000 parts of indoleacrylic acid or its salt
1200 parts of phenol 1100-
5-6 parts of oxalic acid
1000 portions of formaldehyde
20-22 parts of triethylamine
10 portions of ammonia water
3000 portions of methanol and 4200 portions
30-40 parts of titanium dioxide.
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