Biodegradable curing agent, resin, preparation method of resin, resin composition and copper-clad plate
By using biodegradable plant-derived curing agents and resins, the copper clad plate can degrade under acidic conditions, solving the problem of difficult degradation of copper clad plates in the prior art, and achieving environmentally friendly and economical recycling and reuse.
Patent Information
- Application Number
- CN202510094064.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-21
- Publication Date
- 2025-05-30
AI Technical Summary
The existing copper clad plate is difficult to degrade, resulting in high after-treatment costs, serious environmental pollution, and inconvenient recycling.
Biodegradable curing agents and resins are used to degrade their spirocondensation under acidic conditions, and the recycling and reuse of polymer materials are achieved. The curing agent and resin are derived from renewable plants, reducing the use of non-renewable materials.
The degradability of copper clad plate is achieved, the after-treatment cost is reduced, the environmental friendliness is increased, and the recycling and reuse is facilitated.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of manufacturing copper clad laminates, and particularly to a biodegradable curing agent, resin and preparation method thereof, as well as a resin composition and a copper clad laminate comprising the above-mentioned biodegradable curing agent and resin. Background Art
[0002] Copper clad laminates are mainly used for manufacturing printed circuit boards and are widely used in fields such as communication, mobile communication, computers, instruments, satellites, radars, solar cells, flat panel displays, automobiles, etc., mainly playing roles such as component loading, circuit interconnection, and insulation between circuits.
[0003] There are many types of copper clad laminates. For example, rigid copper clad laminates and flexible copper clad laminates. Among rigid copper clad laminates, according to different substrates, they can be further divided into glass fiber cloth substrates, paper substrates, composite substrates, and metal substrates. The commonly used FR4 copper clad laminate belongs to the glass cloth substrate; according to different required functions, copper clad laminates of types such as high-speed copper clad laminates have been developed at present.
[0004] Copper clad laminates are generally formed by laminating multiple prepregs and covering a copper foil on each of the upper and lower sides; the prepregs of copper clad laminates are generally obtained by impregnating reinforcing materials (such as limiting glass cloth, etc.) in a glue solution formed by resin materials (phenolic resin, epoxy resin, polytetrafluoroethylene, etc.), curing agents, etc. After sufficient impregnation, they are dried and cured; the cured prepregs are hard and durable and can withstand a wide range of environmental conditions. However, this also makes them difficult to degrade, remove, recycle, and reuse; currently, the commonly used treatment methods include wet treatment (such as pickling, corrosion, etc.), thermal treatment (incineration, pyrolysis, etc.), and physical and mechanical treatment (crushing, sorting, etc.), but these methods all have their own limitations. Wet treatment and thermal treatment cause serious environmental pollution and require a large investment in environmental protection costs. Physical and mechanical treatment cannot recycle fibers and resins. Therefore, developing a degradable copper clad laminate will greatly reduce the post-treatment cost of copper clad laminates and increase environmental friendliness. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to provide a biodegradable curing agent, resin and preparation method thereof, resin composition, and copper clad laminate. Among them, the curing agent and resin are derived from renewable plants and have degradation properties. The resin composition and copper clad laminate prepared by using them can be degraded, are environmentally friendly, and are convenient for recycling and reuse.
[0006] To solve the above technical problem, the first aspect of the present invention is to provide a curing agent I having the structure of formula I:
[0007]
[0008]
[0009] In Formula I, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclic group, heterocycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl, alkynyl, alkylene, alkylene heteroalkylene, alkenylene, alkylene heteroalkenylene, alkynylene heteroalkynylene, alkynylene or alkylene heteroalkynylene. Preferably, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched-chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted heteroaryl.
[0010] The curing agent I having the structure of Formula I provided by the present invention has terminal hydroxyl groups for reacting with epoxy resin to function as a curing agent. The spiroacetal structure it has enables degradation under acidic conditions, so that the polymer material using the curing agent I can be degraded under acidic conditions, facilitating recycling and reuse without harming the environment; and its physical properties meet the usage requirements; in addition, the compound of Formula I can be derived from plants such as vanilla, belonging to bio-based renewable materials, reducing the use of non-renewable materials and being beneficial to alleviating the energy crisis.
[0011] In the curing agent I provided by the present invention, when selecting R 1 and R 2 , the solubility of the compound of Formula I in common glue solvents such as acetone is preferably considered. When R 1 and R 2 are different, the solubility of the compound of Formula I is too high; at the same time, considering the steric hindrance effect, the substituents are not easily selected to be too large.
[0012] To solve the above technical problems, the second aspect of the present invention is to provide a preparation method of the curing agent I, and this preparation method uses the compounds of Formula II and Formula III as reaction raw materials:
[0013]
[0014] In Formula II, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclic group, heterocycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl, alkynyl, alkylene, alkylene heteroalkylene, alkenylene, alkylene heteroalkenylene, alkynylene heteroalkynylene, alkynylene or alkylene heteroalkynylene. Preferably, R 1 and R 2Independently selected from any one or a combination of more than one of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched-chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted heteroaryl.
[0015] Specifically, the compound of formula II and the compound of formula III are refluxed under the action of a catalyst in an inert gas atmosphere, and after the reaction is completed, the compound of formula I, that is, curing agent I, is obtained by purification. The molar ratio of the compound of formula II to the compound of formula III is greater than 2:1, such as 2.5:1, 3:1, 3.5:1, 4:1, etc.; the reaction time is 5-20 h or 10-15 h or 12 h, preferably 12 h; the reaction temperature is 40 °C-90 °C; the catalyst is p-toluenesulfonic acid, and its dosage is preferably 2 wt% of the total amount of the compounds of formula II and formula III; the inert atmosphere can be, for example, a nitrogen atmosphere; the purification is carried out, for example, by a precipitation method. A 3 wt% sodium bicarbonate solution is added to the product after the reaction is completed to cause precipitation, and curing agent I is obtained after filtration and washing.
[0016] In the preparation method of curing agent I provided by the present invention, the reaction raw materials are from plants (vanilla), which are renewable materials. The curing agent I prepared therefrom belongs to a bio-based degradable curing agent; and the preparation method is easy to operate and convenient for industrial application.
[0017] In order to solve the above technical problems, the third aspect of the present invention is to provide a curing agent II having the structure of formula IV:
[0018]
[0019] In formula IV, R 1 and R 2 are independently selected from any one or a combination of more than one of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclic group, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic group, heteroaromatic group, alkane heteroalkyl, alkynyl, alkylene, alkane heteroalkylene, alkenylene, alkane heteroalkenylene, alkynyl heteroalkenylene, alkynylene or alkane heteroalkynylene; X is none, or selected from -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, C=O, O=S=O; the value range of n can be 1-10 or 2-4. Preferably, R 1 and R 2Independently selected from any one or a combination of more than one of hydrogen, methoxy group, substituted or unsubstituted C1-C8 straight-chain alkyl group, substituted or unsubstituted C1-C8 branched-chain alkyl group, substituted or unsubstituted C3-C8 cycloalkyl group, substituted or unsubstituted C6-C14 aryl group, and substituted or unsubstituted heteroaryl group.
[0020] The curing agent I with the structure of formula I provided by the present invention has terminal hydroxyl groups for reacting with epoxy resins to act as a curing agent. The spiroacetal structure it has can achieve degradation under acidic conditions, so that the polymer material using the curing agent I can be degraded under acidic conditions, which is convenient for recycling and reuse and does not cause harm to the environment; and its physical properties meet the usage requirements; in addition, the compound of formula I can be derived from plants such as vanilla, belonging to bio-based renewable materials, reducing the use of non-renewable materials and being beneficial to alleviating the energy crisis.
[0021] For the curing agent II provided by the present invention, the number of repeating units (i.e., the value of n) is generally 1-10, and the larger the value of n, the larger the viscosity value.
[0022] In order to solve the above technical problems, the fourth aspect of the present invention is to provide a preparation method of the curing agent II, which uses the curing agent I and the compound of formula V as reaction raw materials:
[0023]
[0024] In formula V, X is none, or selected from -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, C=O, O=S=O;
[0025] The curing agent I is selected from the compound of formula I in claim 1 or 2.
[0026] Specifically, curing agent I and the compound of formula V react under the action of a catalyst in an inert gas atmosphere. After the reaction, the compound of formula IV, that is, curing agent II, is obtained by purification. More specifically, the molar ratio of the compound of formula I to the compound of formula V is 1.5 - 5:1 or 2 - 4:1; the reaction temperature is 110 - 180 °C, preferably 155 °C, and the reaction time is 24 h; the catalyst is a mixture of potassium carbonate and 18 - crown - 6, wherein the molar ratio of potassium carbonate to the compound of formula I is 1 - 1.5:1, and the molar ratio of 18 - crown - 6 to the compound of formula I is 0.02 - 0.1:1 or 0.04 - 0.06:1; in the present invention, the molar ratio of curing agent I to the compound of formula V is preferably 2 - 4:1 to ensure that the functional group at the end of the product curing agent II is a hydroxyl group. If the molar ratio is too small, it cannot be ensured to be a hydroxyl group; the inert atmosphere can be, for example, a nitrogen atmosphere; the purification can be, for example, precipitation in pure water, followed by washing with methanol, acetone, and ethyl acetate in sequence to obtain curing agent II. It should be noted that the control of the degree of polymerization n of curing agent II can be achieved by adjusting the molar ratio of the reaction raw materials. The relatively larger the amount of curing agent I input, the larger the value of n.
[0027] The curing agent II provided by the present invention is polymerized from curing agent I and the compound of formula V. Therefore, its raw materials are also renewable raw materials, and the preparation method of curing agent II is easy to operate and convenient for industrial application.
[0028] To solve the above - mentioned technical problems, the fifth aspect of the present invention is to provide a resin I having the structure of formula VI:
[0029]
[0030] In VI, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclic group, heterocyclic alkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl, alkynyl, alkylene, alkylene - hetero - alkylene, alkenylene, alkylene - hetero - alkenylene, alkynylene - hetero - alkenylene, alkynylene, or alkylene - hetero - alkynylene; R 3 is a group containing a terminal double bond. Preferably, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1 - C8 straight - chain alkyl, substituted or unsubstituted C1 - C8 branched - chain alkyl, substituted or unsubstituted C3 - C8 cycloalkyl, substituted or unsubstituted C6 - C14 aryl, and substituted or unsubstituted heteroaryl; R 3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate group, and methacrylate group
[0031] The structure of Resin I provided by the present invention is similar to that of polyphenylene ether. During the subsequent production of copper clad laminates, when the two are compounded and used, they have excellent compatibility; meanwhile, polyphenylene ether is used to provide excellent electrical properties, and Resin I provides degradability; the same spiroacetal structure of Resin I and Curing Agent I enables degradation under acidic conditions, so that the polymer material using Resin I can be degraded under acidic conditions, achieving recycling and causing no harm to the environment; and its physical properties meet the usage requirements.
[0032] To solve the above technical problems, the sixth aspect of the present invention is to provide a preparation method of Resin I, using Curing Agent I and Compound VII as reaction raw materials:
[0033]
[0034] In Formula VII, X is Cl or Br;
[0035] R 3 is a group containing a terminal double bond, preferably selected from one of vinylbenzyl, vinyl, allyl, acrylate group, and methacrylate group;
[0036] Curing Agent I is a compound of Formula I.
[0037] Specifically, Curing Agent I and Compound VII react under an inert gas atmosphere and under alkaline conditions. After the reaction is completed, it is cooled to room temperature, and then post-treated to obtain Compound VII, that is, Resin I. More specifically, the molar ratio of Curing Agent I to Compound VII is 1.5 - 5:1 or 2 - 4:1, and 2 - 4:1 is the preferred molar ratio; the reaction temperature is 50°C - 80°C or 55°C - 65°C or 60°C, and 55°C - 65°C or 60°C is the preferred reaction temperature, and 60°C is the more preferred reaction temperature; the reaction time is 5 - 12 hours or 7 - 10 hours or 8 hours, and 7 - 10 hours or 8 hours is the preferred reaction time, and 8 hours is the more preferred reaction time; the pH value of the reaction system is preferably greater than 14. The inert atmosphere can be, for example, a nitrogen atmosphere; the post-treatment is, for example, filtering and removing the generated salt, and after drying treatment, Resin I is obtained.
[0038] In the preparation method of Resin I provided by the present invention, the raw materials for preparing Curing Agent I in the reaction raw materials come from plants (vanilla), which are renewable materials. The Curing Agent I prepared therefrom belongs to a kind of bio-based degradable curing agent, and the subsequently prepared Resin I also belongs to a kind of bio-based degradable curing agent; and the preparation method is easy to operate and convenient for industrial application.
[0039] To solve the above technical problems, the seventh aspect of the present invention is to provide a Resin II having a structure of Formula VIII:
[0040]
[0041] In Formula VIII, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclic group, heterocycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkheteroalkyl, alkynyl, alkylene, alkheteroalkylene, alkenylene, alkheteroalkenylene, alkynheteroalkenylene, alkynylene or alkheteroalkynylene; X is -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, C=O, O=S=O; R 3 is a group containing a terminal double bond; the value range of n can be 1 - 10 or 2 - 4. Preferably, R 1 and R 2 are each independently selected from one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1 - C8 straight-chain alkyl, substituted or unsubstituted C1 - C8 branched-chain alkyl, substituted or unsubstituted C3 - C8 cycloalkyl, substituted or unsubstituted C6 - C14 aryl and substituted or unsubstituted heteroaryl; R 3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate group and methacrylate group.
[0042] To solve the above technical problems, the eighth aspect of the present invention is to provide a preparation method of Resin II, using curing agent II and the compound of Formula VII as reaction raw materials:
[0043]
[0044] In Formula VII, X is Cl or Br;
[0045] R 3 is a group containing a terminal double bond;
[0046] The curing agent II is the compound of Formula IV in Claim 7 or 8.
[0047] Specifically, curing agent II and the compound of formula VII are reacted under alkaline conditions in an inert gas atmosphere. After the reaction is completed, it is cooled to room temperature, and resin II is obtained through post-treatment. More specifically, the molar ratio of curing agent II to the compound of formula VII is 1.5 - 5:1 or 2 - 4:1, with 2 - 4:1 being the preferred molar ratio; the reaction temperature is 50°C - 80°C or 55°C - 65°C or 60°C, where 55°C - 65°C or 60°C is the preferred reaction temperature, and 60°C is the more preferred reaction temperature; the reaction time is 5 - 12 hours or 7 - 10 hours or 8 hours, where 7 - 10 hours or 8 hours is the preferred reaction time, and 8 hours is the more preferred reaction time; the pH value of the reaction system is preferably greater than 14. The inert atmosphere can be, for example, a nitrogen atmosphere; for post-treatment, for example, the generated salt is filtered off and after drying treatment, resin II is obtained.
[0048] In the preparation method of resin II provided by the present invention, curing agent II is included in the reaction raw materials, and the raw materials of curing agent II include curing agent I. The raw materials for preparing curing agent I are derived from plants (vanilla), which are renewable materials. The curing agent I prepared therefrom belongs to a bio-based degradable curing agent, and thus the resin II prepared therefrom also belongs to a bio-based degradable curing agent; moreover, the preparation method is easy to operate and convenient for industrial application.
[0049] To solve the above technical problems, the ninth aspect of the present invention is to provide a resin composition I, whose raw material composition includes the following components in parts by mass:
[0050] Epoxy resin: 20 - 60 parts by mass;
[0051] Curing agent I and / or curing agent II: 20 - 70 parts by mass.
[0052] In the resin composition provided by the present invention, the curing agent includes curing agent I and / or curing agent II, both of which are bio-based degradable curing agents, and the reaction raw materials are renewable raw materials. The prepreg prepared from this resin composition can be degraded; the epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, MDI-modified epoxy resin, DCPD epoxy resin, multi-functional epoxy resin; preferably, in resin composition I, a non-degradable curing agent can also be added, such as a phosphorus-containing curing agent, an amine curing agent, a phenolic curing agent, an acid anhydride curing agent, an ester curing agent, an imidazole curing agent or a mercaptan, etc. to improve flame retardancy, balance mechanical properties, etc.; in addition, when this resin composition is used to prepare a prepreg, it can also include conventional components such as a catalyst, a flame retardant, a silane coupling agent, a dispersant, an inorganic filler, etc. The catalyst is, for example, one or more of an imidazole catalyst, an organic cobalt complex catalyst, an organic copper complex catalyst, an organic zinc complex catalyst or an organic iron complex catalyst, preferably an imidazole catalyst; the inorganic filler is, for example, one or more of aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talcum powder, alumina, barium sulfate, barium titanate, strontium titanate, core-shell rubber, calcium carbonate or titanium dioxide; other conventional components can be added as needed.
[0053] To solve the above technical problems, the tenth aspect of the present invention is to provide a copper clad laminate I, the prepreg of which is made of resin composition I. It can be understood that since resin composition I contains curing agent I and / or curing agent II, it is easy to be degraded, and the physical properties tested meet the application requirements; among them, too little addition amount of curing agent I and / or curing agent II will cause the copper clad laminate to be not easily degraded. The preferred addition amount is 20-70 parts by mass. At the same time, the specific ratio of the epoxy resin to the curing agent is generally calculated according to the epoxy equivalent and the equivalent of the reaction group of the curing agent. The specific general proportional relationship is 1:1. The copper clad laminate I can be used as an FR4 copper clad laminate, for example.
[0054] To solve the above technical problems, the eleventh aspect of the present invention is to provide a resin composition II, the raw material composition of which includes the following components in parts by mass:
[0055] Resin I and / or resin II: 20-50 parts by mass;
[0056] Polyphenylene ether: 10-50 parts by mass;
[0057] Unsaturated double bond crosslinking type curing agent 5-30 parts by mass.
[0058] In the resin composition II provided by the present invention, the unsaturated double bond crosslinking curing agents include TAIC, DVB, BMI-3000J, MIR3000, etc.; the polyphenylene ether can be, for example, a methyl methacrylate-modified polyphenylene ether (Sabic SA9000), a phenyl vinyl-modified polyphenylene ether (MGC OPE-2st), etc. In this resin composition, resin I and / or resin II are structurally similar to the polyphenylene ether, and thus have good compatibility; in addition, the polyphenylene ether has excellent electrical properties, and resin I and / or resin II have degradability. The resin composition formed by compounding the two can not only ensure excellent physical property indexes but also have good degradability; it should be noted that when this resin composition is used to prepare a prepreg, it can also include conventional components such as catalysts, flame retardants, silane coupling agents, dispersants, and inorganic fillers. The catalysts can be, for example, one or more of imidazole catalysts, organic cobalt complex catalysts, organic copper complex catalysts, organic zinc complex catalysts, or organic iron complex catalysts, preferably imidazole catalysts; the inorganic fillers can be, for example, one or more of aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talcum powder, alumina, barium sulfate, barium titanate, strontium titanate, core-shell rubber, calcium carbonate, or titanium dioxide; other conventional components can be added as needed.
[0059] To solve the above technical problems, the twelfth aspect of the present invention is to provide a copper clad laminate II, the prepreg of which is prepared from the resin composition II. Understandably, since the resin composition II contains resin I and / or resin II, it is easily degradable, and the polyphenylene ether ensures the excellent electrical properties of the copper clad laminate. After testing, the physical property indexes of the copper clad laminate II meet the usage requirements; the copper clad laminate II can be used as a high-speed copper clad laminate, for example.
[0060] In addition, the preparation processes of the copper clad laminates I and II are, for example, first weighing the raw materials of the resin composition in a solution according to the required parts by weight to form a glue solution; then impregnating the glass fiber cloth in the glue solution, and baking after impregnation is completed to obtain a prepreg; taking multiple prepregs and laminating them, covering copper foils on the upper and lower surfaces respectively, and finally hot pressing to obtain the copper clad laminate. This can be obtained by existing technologies and will not be elaborated here. Description of the Drawings
[0061] To more clearly illustrate the technical solutions of the present invention, the drawings required for the present invention will be briefly introduced below.
[0062] Figure 1 It is the characterization result of the curing agent I prepared in Example 1;
[0063] Figure 2 It is the characterization result of the curing agent II prepared in Example 2. Detailed Embodiments
[0064] The technical solutions in the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts belong to the scope of protection of the present invention.
[0065] Preparation of Curing Agent I in Example 1
[0066] Reaction raw materials: Compound of Formula II (vanilla extract, commercially available); Compound of Formula III (vanilla extract, commercially available); p-toluenesulfonic acid (commercially available);
[0067]
[0068] Preparation method: Take 40 g of the compound of Formula II, 18 g of the compound of Formula III, 165 ml of N,N-dimethylformamide, and 180 ml of petroleum ether in a reflux reactor. Add 1.12 g of p-benzenesulfonic acid, and introduce nitrogen to maintain an inert gas atmosphere. Heat to 90 °C and reflux for 12 h; pour the reaction solution into 1 L of 3 wt% sodium bicarbonate solution. The obtained precipitate is filtered and dried to obtain the product of Curing Agent I, and the characterization results are as Figure 1 shown. Among them, the hydroxyl equivalent is 180 - 250 g / eq.
[0069] Preparation of Curing Agent II in Example 2
[0070] Reaction raw materials: Curing Agent I (prepared in Example 1), Compound of Formula V (commercially available), potassium carbonate (commercially available), 18-crown-6 (commercially available);
[0071]
[0072] Preparation method: Take 8.08 g of Curing Agent I, 4.36 g of the compound of Formula V, 3.45 g of potassium carbonate, 0.27 g of 18-crown-6, and 100 ml of dimethyl sulfoxide in a reaction vessel. React at 155 °C for 24 hours under a nitrogen environment. Pour the reaction solution into 1 L of a methanol / water 1 / 1 (vol / vol) mixed solution. The obtained precipitate is filtered and dried to obtain the product of Curing Agent II. Figure 2 shown, among which, the hydroxyl equivalent is 330 - 400 g / eq.
[0073] Preparation of Resin I in Example 3
[0074] Reaction raw materials: Curing Agent I (prepared in Example 1), Compound of Formula VII (commercially available), potassium carbonate (commercially available);
[0075]
[0076] In Formula VII, X is Br.
[0077] Preparation method: Take 8.08 g of curing agent I and 5.36 g of potassium carbonate, dissolve them in 100 ml of N,N-dimethylformamide at 0 °C, and then add 2.42 g of 3-bromo-1-propene to the above solvent in a slow dropping manner. After reacting at 25 °C for 24 hours in a nitrogen environment, add 50 ml of pure water to the reaction vessel to terminate the reaction, extract with 50 ml of ethyl acetate three times, wash the organic phase with 100 ml of saturated brine three times, dry the organic phase with anhydrous magnesium sulfate, and then vacuum dry to obtain the resin I product.
[0078] Preparation of Resin II in Example 4
[0079] Reaction raw materials: Curing agent II (prepared in Example 2), compound of Formula VII (commercially available), potassium carbonate (commercially available);
[0080]
[0081] In Formula VII, X is Br.
[0082] Preparation method: Take 16.16 g of curing agent II and 5.36 g of potassium carbonate, dissolve them in 300 ml of N,N-dimethylformamide at 0 °C, and then add 2.42 g of 3-bromo-1-propene to the above solvent in a slow dropping manner. After reacting at 25 °C for 24 hours in a nitrogen environment, add 50 ml of pure water to the reaction vessel to terminate the reaction, extract with 50 ml of ethyl acetate three times, wash the organic phase with 100 ml of saturated brine three times, dry the organic phase with anhydrous magnesium sulfate, and then vacuum dry to obtain the resin II product.
[0083] Preparation of FR4 Copper Clad Laminate in Example 5
[0084] Preparation of adhesive solution: Take bisphenol A epoxy resin (Dow DER331, epoxy equivalent 182 - 192 g / eq), curing agent I and / or curing agent II (prepared in the previous examples), phosphorus-containing curing agent (phosphorus-containing phenolic resin, Shin-A LC950PM60, hydroxyl equivalent 320 - 360 g / eq), toughening agent (SEBS, KRATON MD6951M), silica powder (spherical silica, Union Rui NQ1020B), flame retardant (phosphorus-containing flame retardant, Clariant OP935) and catalyst (2-phenylimidazole) in acetone to obtain the adhesive solution. The component ratios are shown in Table 1.
[0085] Table 1
[0086] Category Experimental Group 1 Experimental Group 2 Experimental Group 3 Control Group 1 Control Group 2 A: Epoxy Resin 46 35 35 35 35 B: Curing Agent I 54 5 C: Curing Agent II 65 50 D: Phosphorus-containing Curing Agent 15 65 60 E: Toughness Agent 3 3 3 3 3 F: Silica Powder 40 40 40 40 40 G: Flame Retardant 15 15 15 15 15 H: Catalyst 0.05 0.05 0.05 0.05 0.05 I: Solvent 15 15 15 15 15
[0087] Preparation of prepreg: The glass fiber cloth is impregnated in the aforementioned adhesive solution. After impregnation, it is baked at a temperature of 120 - 170 °C for 3 - 9 minutes to obtain the prepreg;
[0088] Preparation of copper clad laminate: Take 8 prepregs, stack them, cover copper foils on the upper and lower surfaces respectively, and then perform hot pressing to obtain the copper clad laminate.
[0089] Among them, the copper clad laminates obtained in Experimental Groups 1 - 3 contain bio - based and biodegradable curing agent I and curing agent II. The copper clad laminates obtained in Control Groups 1 and 3 do not contain bio - based and biodegradable curing agents and are copper clad laminates of the prior art.
[0090] Preparation of High - speed Copper Clad Laminate in Example Six
[0091] Preparation of adhesive solution: Polyphenylene ether (SABIC SA - 9000), Resin I (prepared in Example Three above) and / or Resin II (prepared in Example Four above), cross - linker (Mitsubishi Chemical TAIC), toughening agent (SEBS, KRATON MD6951M), silica powder (Admatch SC - 2300), flame retardant (Albemarle Chemical HP - 8010) and catalyst (NOF Corporation PERHEXA 25B) are dissolved in a mixed solvent of acetone and butanone to obtain the adhesive solution. The component ratios are shown in Table 2.
[0092] Table 3
[0093] Category Experimental Group 4 Experimental Group 5 Experimental Group 6 Control Group 3 Control Group 4 A: Polyphenylene Oxide 50 30 30 80 75 B: Resin 1 30 50 5 C: Resin 2 50 D: Crosslinking Agent 20 20 20 20 20 E: Toughness Agent 3 3 3 3 3 F: Silica Powder 45 45 45 45 45 G: Flame Retardant 15 15 15 15 15 H: Catalyst 1 1 1 1 1 I: Solvent 20 20 20 20 20
[0094] The preparation method of the copper clad laminate is the same as that in Example Five.
[0095] Example Seven - Test Example
[0096] Test items:
[0097] Glass transition temperature (Tg), measured by testing, with a heating rate of 5 °C / min. Generally speaking, the higher the Tg, the better;
[0098] CTE(X,Y - α1), measured by TMA tensile method, with a heating rate of 5 °C / min and a test temperature range of 40 - 130. Generally speaking, the smaller the value, the better;
[0099] T288, measured by TMA. Under the condition of 288 °C, the product can maintain no delamination or blistering for more than 60 minutes, indicating that it meets the performance requirements;
[0100] Dielectric properties (dielectric loss factor Df), measured by the flat plate method according to IPC - TM - 650 2.5.5.9, with a test frequency of 1 GHz. Generally, the smaller the value of Df, the better;
[0101] Copper foil peel strength: According to the "after thermal stress" test condition in IPC-TM-650 2.4.8 method, the peel strength of the metal (copper) coating is tested, and the value is generally required to be greater than 1.0 N / cm.
[0102] Degradation: After the copper foil is peeled off, the remaining part is soaked in a 1M HCl solution for degradation, which can achieve degradation and takes a short time.
[0103] The test results of the FR4 copper clad laminate obtained in Example 5 are shown in Table 3, and the test results of the high-speed copper clad laminate obtained in Example 6 are shown in Table 4:
[0104] Table 3
[0105]
[0106] Table 4
[0107]
[0108] From the test results of the FR4 copper clad laminate, it can be seen that the copper clad laminates prepared in Experimental Groups 1-3 can achieve degradation under acidic conditions, and the fastest degradation time can reach within 48 hours, while Comparative Groups 1 and 2 without the bio-based degradable curing agent cannot achieve degradation; other test items show that the physical property indexes of the copper clad laminate added with the bio-based degradable curing agent meet the application requirements.
[0109] From the test results of the high-speed copper clad laminate, it can be seen that the copper clad laminates prepared in Experimental Groups 4-6 can achieve degradation under acidic conditions, and the fastest degradation time can reach within 72 hours, while Comparative Groups 3 and 4 without the bio-based degradable curing agent cannot achieve degradation; other test items show that the physical property indexes of the copper clad laminate added with the bio-based degradable curing agent meet the application requirements.
[0110] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention.
Claims
1. A curing agent I, characterized in that: Having the structure of Formula I: In Formula I, R1 and R2 are independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene-heteroalkenylene, alkynylene or alkylene-heteroalkynylene.
2. The curing agent I as claimed in claim 1, characterized in that R1 and R2 are independently selected from any one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl and substituted or unsubstituted heteroaryl.
3. A method for preparing the curing agent I as claimed in claim 1 or 2, characterized in that: The compounds of formula II and formula III are used as the reaction raw materials: In Formula II, R1 and R2 are independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene-heteroalkenylene, alkynylene or alkylene-heteroalkynylene.
4. The method according to claim 3, characterized in that R1 and R2 are independently selected from any one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl and substituted or unsubstituted heteroaryl.
5. The method according to claim 3, characterized in that The compound of formula II and the compound of formula III are subjected to reflux reaction in an inert gas atmosphere under the action of a catalyst, and after the reaction is completed, the compound of formula I, i.e., curing agent I, is purified, wherein the molar ratio of the compound of formula II to the compound of formula III is greater than 2:
1.
6. The preparation method according to claim 5, characterized in that: The reaction time is 5-20h or 10-15h or 12h; The reaction temperature is 40°C-90°C; The catalyst is p-toluenesulfonic acid.
7. A curing agent II, characterized in that: Has the structure of Formula IV: In formula IV, R1 and R2 are independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclyl, heterocyclalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene-heteroalkenylene, alkynylene or alkylene-heteroalkynylene; X is none or selected from one of -CH2-, -CH(CH3)-, -C(CH3)2-, C=O, O=S=O; and n can range from 1 to 10 or from 2 to 4.
8. The curing agent II as claimed in claim 7, characterized in that R1 and R2 are independently selected from any one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted heteroaryl.
9. A method for preparing the curing agent II as claimed in claim 7 or 8, characterized in that: Take curing agent I and compound of formula V as reaction raw materials: In formula V, X is none, or is selected from one of -CH2-, -CH(CH3)-, -C(CH3)2-, C=O, O=S=O; The curing agent I is selected from the compounds of formula I according to claim 1 or 2.
10. The preparation method according to claim 9, characterized in that: The curing agent I and the compound of formula V react in an inert gas atmosphere under the action of a catalyst, and after the reaction is completed, the compound of formula IV, namely the curing agent II, is purified.
11. The preparation method according to claim 7, characterized in that: The molar ratio of the compound of formula I to the compound of formula V is 1.5-5:1 or 2-4:1; The reaction temperature is 110-120°C; The catalyst is a mixture of potassium carbonate and 18-crown ether-6, wherein the molar ratio of potassium carbonate to the compound of formula I is 1-1.5:1, and the molar ratio of 18-crown ether-6 to the compound of formula I is 0.02-0.1:1 or 0.04-0.06:
1.
12. A resin I, characterized in that Has the structure of Formula VI: In VI, R1 and R2 are independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene-heteroalkenylene, alkynylene or alkylene-heteroalkynylene; and R3 is a group containing a terminal double bond.
13. The resin I according to claim 12, characterized in that R1 and R2 are independently selected from any one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted heteroaryl; R3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate and methacrylate.
14. A method for preparing the resin I according to claim 12 or 13, characterized in that: Take curing agent I and compound of formula VII as reaction raw materials: X-R3 Formula VII In formula VII, X is Cl or Br; R3 is a group containing a terminal double bond; The curing agent I is selected from the compounds of formula I according to claim 1 or 2.
15. The preparation method according to claim 14, characterized in that: The curing agent I and the compound of formula VII react in an inert gas atmosphere under alkaline conditions. After the reaction is completed, the mixture is cooled to room temperature and post-treated to obtain the compound of formula VII, namely, resin I.
16. The preparation method according to claim 15, characterized in that: The molar ratio of curing agent I to the compound of formula VII is 1.5-5:1 or 2-4:1; The reaction temperature is 50°C-80°C or 55°C-65°C or 60°C; The reaction time is 5-12 hours or 7-10 hours or 8 hours; The pH value of the reaction system is >14; R3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate and methacrylate.
17. A resin II, characterized in that Having the structure of formula VIII: In formula VIII, R1 and R2 are independently selected from one or more combinations of hydrogen, methoxy, alkyl, cycloalkyl, heterocyclyl, heterocyclalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene-heteroalkenylene, alkynylene or alkylene-heteroalkynylene; X is one of -CH2-, -CH(CH3)-, -C(CH3)2-, C=O, O=S=O; R3 is a group containing a terminal double bond; and n can range from 1 to 10 or 2 to 4.
18. The resin II according to claim 17, characterized in that R1 and R2 are independently selected from any one or more combinations of hydrogen, methoxy, substituted or unsubstituted C1-C8 straight-chain alkyl, substituted or unsubstituted C1-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl and substituted or unsubstituted heteroaryl; R3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate and methacrylate.
19. A method for preparing the resin II according to claim 17 or 18, characterized in that: Take curing agent II and compound of formula VII as reaction raw materials: X-R3 Formula VII In formula VII, X is Cl or Br; R3 is a group containing a terminal double bond; The curing agent II is a compound of formula IV according to claim 7 or 8.
20. The preparation method according to claim 19, characterized in that: The curing agent II and the compound of formula VII are reacted in an inert gas atmosphere under alkaline conditions. After the reaction is completed, the mixture is cooled to room temperature and post-treated to obtain the compound of formula VII, namely, resin I.
21. The preparation method according to claim 20, characterized in that: The molar ratio of curing agent II to the compound of formula VII is 1.5-5:1 or 2-4:1; The reaction temperature is 50°C-80°C or 55°C-65°C or 60°C; The reaction time is 5-12 hours or 7-10 hours or 8 hours; The pH value of the reaction system is >14; R3 is selected from one of vinylbenzyl, vinyl, allyl, acrylate and methacrylate.
22. A resin composition I, characterized in that The raw material composition includes the following components by mass: Epoxy resin: 20-60 parts by mass; Curing agent I and / or curing agent II: 20-70 parts by mass.
23. The resin composition according to claim 22, characterized in that The optional range of epoxy resins includes bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, phosphorus-containing epoxy resin, bromine-containing epoxy resin, MDI-modified epoxy resin, DCPD epoxy resin, and multifunctional epoxy resin.
24. A copper clad laminate I, characterized in that: The semi-cured sheet is made of the resin composition I described in claim 22.
25. A resin composition II, characterized in that: The raw material composition includes the following components by mass: Resin I and / or resin II: 20-50 parts by mass; Polyphenylene ether: 10-50 parts by mass; 5-30 parts by weight of unsaturated double bond cross-linking curing agent.
26. A copper clad laminate II, characterized in that: The semi-cured sheet is made of the resin composition II described in claim 25 as a raw material.