CN115044016B - Halogen-free epoxidized soybean oil modified resin and preparation method and application thereof - Google Patents

Halogen-free epoxidized soybean oil modified resin and preparation method and application thereof Download PDF

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CN115044016B
CN115044016B CN202210811104.5A CN202210811104A CN115044016B CN 115044016 B CN115044016 B CN 115044016B CN 202210811104 A CN202210811104 A CN 202210811104A CN 115044016 B CN115044016 B CN 115044016B
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soybean oil
epoxidized soybean
halogen
resin
free
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CN115044016A (en
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张龙
李龙
李莎
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Shengyi Technology Shaanxi Co ltd
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Shengyi Technology Shaanxi Co ltd
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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  • Engineering & Computer Science (AREA)
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  • Materials Engineering (AREA)
  • Epoxy Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a halogen-free epoxidized soybean oil modified resin, and a preparation method and application thereof, wherein the preparation raw materials of the halogen-free epoxidized soybean oil modified resin comprise epoxidized soybean oil, C12-C20 fatty acid and polyamine; the epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the intermediate reacts with polyamine to obtain the halogen-free epoxidized soybean oil modified resin. The halogen-free epoxy soybean oil modified resin contains a flexible long carbon chain structure and proper branching degree, improves the toughness of a resin cured product, can keep the heat resistance of the resin cured product at a high level, does not contain halogen, and is environment-friendly. The preparation process of the halogen-free epoxidized soybean oil modified resin has the advantages of mild conditions, easiness in operation, wide raw material sources and low cost, and is suitable for large-scale industrial mass production. The resin composition and the copper-clad plate containing the halogen-free epoxidized soybean oil modified resin have excellent toughness and impact resistance and high T g And excellent heat resistance.

Description

Halogen-free epoxidized soybean oil modified resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to halogen-free epoxy soybean oil modified resin, and a preparation method and application thereof.
Background
A printed circuit board (Printed Circuit Board, PCB) is a member for electrical connection in electronic equipment and electronic components, and is one of important electronic materials; the PCB is typically manufactured by processing a copper clad laminate through different processes. Therefore, the quality, service life, manufacturing level and the like of the PCB depend on the performance of the copper-clad plate to a great extent.
Copper-clad laminates generally include a substrate having a reinforcing effect and a resin layer bonded to the substrate, the most common resin layer at present being an epoxy resin system. The epoxy resin has good mechanical property, good cohesiveness, small shrinkage, good corrosion resistance and better technological property. However, epoxy resins are brittle after curing, have poor impact resistance, and are prone to cracking, which limits their use. Therefore, in order to reduce the brittleness of the epoxy cured product and improve the toughness of the epoxy resin cured product so as to meet the processing application requirements, a great deal of intensive work has been done on the research of toughening agents, and a series of epoxy resin toughening agents have been developed. The ideal toughening agent has the advantages of improving the impact resistance of the epoxy resin condensate, having the least influence on other properties and having the cost advantage.
The epoxidized soybean oil is an aid widely used in plastic processing, mainly plays a role in plasticization and stabilization, has a certain toughening effect, and is expected to be used in an epoxy resin system. For example, CN104557795a discloses a preparation method of epoxidized soybean oil oligomer for electronic grade copper-clad plate toughening agent, the raw materials include: 100 parts of epoxidized soybean oil, 1.5-5 parts of diethylenetriamine and/or N, N-dimethylbenzylamine; in the preparation process, epoxidized soybean oil, diethylenetriamine and N, N-dimethylbenzylamine are sequentially added into a reactor for reaction, so that the epoxidized soybean oil oligomer is obtained. The epoxidized soybean oil oligomer is used for preparing the copper-clad laminate of electronic grade products, has a certain toughening effect, but has limited toughening effect, and has poor compatibility with main epoxy resin, thereby affecting the heat resistance and reliability of the epoxy resin cured product and the copper-clad laminate.
CN113061223a discloses a preparation method of epoxy soybean oil modified resin, adding epoxy soybean oil, bisphenol a and cardanol after epoxy ring opening into a reaction kettle for addition reaction, adding melamine, formaldehyde and phenol for polycondensation, and gelling the generated product to obtain nitrogen-containing epoxy soybean oil modified resin; the nitrogen-containing epoxidized soybean oil modified resin is mixed with epoxy resin to form glue solution, and the glue solution is used for preparing paper-based copper-clad plates. The nitrogen-containing epoxidized soybean oil modified resin is actually an epoxidized soybean oil modified phenolic resin containing melamine, and because the modified reaction activity of the epoxidized soybean oil on the phenolic resin is low, the conversion rate of epoxy groups is still low even if the epoxy groups react for a long time under alkaline and high-temperature conditions, and therefore, the system contains more suspension chains grafted by etherification and blends in a free state, the heat resistance of the resin is poor, and the performances of an epoxy cured product and a copper-clad plate are further influenced.
CN106433018A discloses a glue solution for a flame-retardant paper-based copper-clad plate and a copper-clad plate, wherein the raw materials of the glue solution comprise epoxy soybean oil modified phenolic resin, epoxy resin, flame retardant and organic solvent; the epoxidized soybean oil modified phenolic resin is prepared from epoxidized soybean oil, phenol, bisphenol A, 2-methylimidazole, formaldehyde, an alkaline catalyst, graphene oxide and the like. The copper-clad plate prepared from the glue solution has poor toughness and certain heat resistance due to insufficient toughening effect of the epoxidized soybean oil modified phenolic resin.
Based on this, development of a toughening agent having both excellent toughening effect and good heat resistance is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the halogen-free epoxy soybean oil modified resin, and the preparation method and the application thereof, wherein the halogen-free epoxy soybean oil modified resin contains a flexible long carbon chain structure and proper branching degree, can remarkably improve the toughness of a resin cured product, can keep the heat resistance of the resin cured product at a higher level, does not contain halogen, and meets the green environment-friendly requirement.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a halogen-free epoxidized soybean oil modified resin, the preparation raw materials of which comprise epoxidized soybean oil, a C12-C20 fatty acid and a polyamine.
And reacting the epoxidized soybean oil with C12-C20 fatty acid to generate an intermediate, and reacting the intermediate with polyamine to obtain the halogen-free epoxidized soybean oil modified resin.
In the halogen-free epoxidized soybean oil modified resin provided by the invention, firstly, the epoxy soybean oil is subjected to esterification grafting reaction by using C12-C20 fatty acid, then the polyamine is used for chain extension, and the halogen-free epoxidized soybean oil modified resin has excellent flexibility and a certain branching degree through introducing a long fatty chain structure and performing effective chain extension. The halogen-free epoxidized soybean oil modified resin is used as a toughening agent, so that not only can the toughness and impact resistance of a resin cured product be effectively improved, but also the heat resistance of the resin cured product can be kept unchanged, and the resin cured product has a higher heat resistance level; meanwhile, the halogen-free epoxy soybean oil modified resin does not contain halogen, and meets the green environment-friendly requirement.
In the present invention, the expression "Ca-Cb" means that the number of carbon atoms in the group is a-b.
The C12-C20 fatty acids include C12, C13, C14, C15, C16, C17, C18, C19, C20 fatty acids. The molecular structure of the C12-C20 fatty acid may contain other optional substituents such as hydroxyl groups, in addition to the linear or branched carbon chain and carboxyl groups.
In the present invention, the polyamine is a compound containing at least 2 (e.g., 2, 3, 4, etc.) amino groups.
Preferably, the epoxidized soybean oil is a commercially available epoxidized soybean oil having an epoxy value of 5.9 to 6.9%, for example, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7% or 6.8%, etc.
Preferably, the C12-C20 fatty acid is a C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, or C19, etc.) saturated fatty acid and/or a C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, or C19, etc.) unsaturated fatty acid, more preferably a C12-C20 saturated fatty acid.
Preferably, the C12-C20 unsaturated fatty acid contains at least one (e.g. 1,2 or 3 etc.) unsaturated bond, including c=c and/or c≡c, preferably c=c.
Preferably, the C12-C20 fatty acid comprises any one or a combination of at least two of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid or arachic acid, and further preferably comprises stearic acid.
Preferably, the molar ratio of the epoxidized soybean oil to the C12-C20 fatty acid is 1 (0.3-0.4), for example, 1:0.31, 1:0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37, 1:0.38 or 1:0.39, etc., and further preferably 1 (0.329-0.399).
Preferably, the polyamine comprises a diamine and/or a triamine, more preferably a diamine.
As a preferred technical scheme of the invention, the polyamine comprises diamine, and the diamine reacts with an intermediate (obtained by reacting epoxidized soybean oil and C12-C20 fatty acid) to effectively chain-extend, so that the halogen-free epoxidized soybean oil modified resin has excellent flexibility and proper branching degree. If the functionality of the polyamine is too high (e.g., a triamine), the reaction process may tend to crosslink, affecting the chain extension of the system, thereby adversely affecting the obtaining of the high flexibility halogen-free epoxidized soybean oil modified resin.
Preferably, the polyamine isR is selected from the group consisting of C1-C10 straight or branched chain alkylene, C6-C20 arylene,/->Any one of the following.
Wherein the C1-C10 linear or branched alkylene includes C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 linear or branched alkylene, exemplary including but not limited to: methylene, 1, 2-ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and the like.
The C6-C20 arylene group includes C6. Arylene groups of C9, C10, C12, C14, C16, or C18, etc., illustratively include, but are not limited to: phenylene groupNaphthylene->Biphenylene radicalsEtc.; * Representing the attachment site of the group.
m 1 、m 2 Represents the number of methylene groups, each independently selected from integers from 0 to 5, for example, may be 0, 1,2, 3, 4 or 5; and m is 1 +m 2 ＞0。
L is selected from any one of-O-, -S-, -SO-, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight-chain or branched-chain alkylene.
* Representing the attachment site of the group.
Preferably, R is selected from the group consisting of C2-C8 straight or branched chain alkylene, Any one of the following.
Preferably, R is a group containing an aromatic functional group, e.g., R is a C6-C20 arylene group,Compared with aliphatic polyamine with R being alkylene, the reaction process of the polyamine containing aromatic functional groups and the intermediate is easy to control, and the heat resistance of the halogen-free epoxidized soybean oil modified resin is improved.
Preferably, the polyamine comprises any one or a combination of at least two of ethylenediamine, hexamethylenediamine, m-phenylenediamine, m-xylylenediamine or diaminodiphenylmethane, and further preferably comprises any one or a combination of at least two of m-phenylenediamine, m-xylylenediamine or diaminodiphenylmethane.
Preferably, the intermediate has an epoxy equivalent of 300-350g/eq, such as 315g/eq, 320g/eq, 325g/eq, 330g/eq, 335g/eq, 340g/eq or 345g/eq, and specific point values between the above point values, are limited in space and for the sake of brevity the invention is not exhaustive.
Preferably, the epoxy equivalent of the halogen-free epoxy soybean oil modified resin is 400-500g/eq, for example, 410g/eq, 420g/eq, 430g/eq, 440g/eq, 450g/eq, 460g/eq, 470g/eq, 480g/eq or 490g/eq, and specific point values between the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
In a second aspect, the present invention provides a method for preparing the halogen-free epoxidized soybean oil modified resin of the first aspect, the method comprising: the epoxidized soybean oil reacts with C12-C20 fatty acid to obtain an intermediate; and reacting the intermediate with polyamine to obtain the halogen-free epoxy soybean oil modified resin.
The preparation method of the halogen-free epoxidized soybean oil modified resin comprises two steps, wherein the first step is to react the epoxidized soybean oil with C12-C20 fatty acid to generate an intermediate, and the reaction formula can be expressed as follows:
wherein R is 1 Representing the fatty chain in the C12-C20 fatty acid, and the wavy line represents the fatty chain in the epoxidized soybean oil or the fatty chain containing an epoxy group. In this step, the epoxidized soybean oil is reacted with a C12-C20 fatty acid to convert a portion of the epoxy groups in the epoxidized soybean oil to ester groups and introduce long fatty chains into the intermediate.
As a preferable technical scheme of the invention, the molar ratio of the epoxidized soybean oil to the C12-C20 fatty acid is 1 (0.3-0.4), and more preferably 1 (0.329-0.399); the epoxy equivalent of the intermediate is preferably 300-350g/eq, and the intermediate is reacted with polyamine to obtain the halogen-free epoxy soybean oil modified resin with excellent flexibility and a certain branching degree, so that the epoxy condensate is endowed with excellent toughness, impact resistance and heat resistance. If the consumption of the C12-C20 fatty acid is too small, the epoxy equivalent of the intermediate is lower, and the flexibility and the toughening effect of the halogen-free epoxy soybean oil modified resin are affected; if the using amount of the C12-C20 fatty acid is too large, the epoxy equivalent of the intermediate is higher, the reaction of the intermediate and the polyamine is affected, the chain extension is insufficient, and the molecular weight of the halogen-free epoxidized soybean oil modified resin is small, and the comprehensive performance is poor.
The second step is the reaction of the intermediate with a polyamine to obtain a halogen-free epoxidized soybean oil modified resin, which illustratively comprises the following structural units:wherein R is 1 Represents a fatty chain in a C12-C20 fatty acid, R represents a group for linking 2 amino groups in a polyamine, and ESO represents a residue after the reaction of epoxidized soybean oil (an epoxy group in epoxidized soybean oil).
As a preferred technical scheme of the invention, the intermediate with the epoxy equivalent weight of 300-350g/eq and polyamine are subjected to chain extension reaction to obtain the halogen-free epoxy soybean oil modified resin (final product) with the epoxy equivalent weight of 400-500g/eq. If the consumption of the polyamine is small and the chain extension reaction is insufficient, the epoxy equivalent of the final product is lower (less than 400 g/eq), the molecular weight of the halogen-free epoxidized soybean oil modified resin is small and the comprehensive performance is poor; if the amount of polyamine is too large, the epoxy equivalent of the halogen-free epoxidized soybean oil modified resin is more than 500g/eq, the reactivity thereof in the composition is poor, and the heat resistance of the epoxy cured product is affected.
Preferably, the reaction of the epoxidized soybean oil with the C12-C20 fatty acid is carried out in the presence of a catalyst.
Preferably, the catalyst comprises any one or a combination of at least two of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole, and further preferably triphenylphosphine.
Preferably, the mass of the catalyst is 0.01 to 0.2%, for example, may be 0.03%, 0.05%, 0.08%, 0.1%, 0.11%, 0.13%, 0.15%, 0.17% or 0.19%, and specific point values between the above point values, based on 100% total mass of the epoxidized soybean oil and the C12-C20 fatty acid, are limited in length and for brevity, the present invention is not exhaustive list of specific point values included in the range.
Preferably, the reaction temperature of the epoxidized soybean oil and the C12-C20 fatty acid is 100-180 ℃, for example, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or 175 ℃, and specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the reaction time of the epoxidized soybean oil and the C12-C20 fatty acid is 0.5 to 8 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours or 7.5 hours, and the specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the reaction temperature of the intermediate with the polyamine is 100-180 ℃, for example, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, or 175 ℃, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the reaction time of the intermediate with the polyamine is 0.5 to 5h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the preparation further comprises the step of adding a diluent.
Preferably, the diluent is added after the reaction of the intermediate with the polyamine is completed.
Preferably, the diluent comprises any one or a combination of at least two of toluene, xylene, acetone or butanone.
Preferably, the preparation method specifically comprises the following steps:
(1) The epoxidized soybean oil reacts with C12-C20 fatty acid in the presence of a catalyst to obtain an intermediate; the catalyst comprises any one or a combination of at least two of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole; the reaction temperature is 100-180 ℃ and the reaction time is 0.5-8h;
(2) Reacting the intermediate obtained in the step (1) with polyamine at 100-180 ℃ for 0.5-5h to obtain the halogen-free epoxidized soybean oil modified resin.
In a third aspect, the present invention provides a resin composition comprising a host resin and a halogen-free epoxidized soybean oil modified resin as described in the first aspect.
Preferably, the host resin comprises an epoxy resin.
As a preferable technical scheme of the invention, the halogen-free epoxy soybean oil modified resin is used for the resin composition taking the epoxy resin as a main body, has good compatibility with the main body resin, can obviously improve the toughness and impact resistance of an epoxy cured product, and keeps the heat resistance of the resin composition at a high level.
Preferably, the epoxy resin is an epoxy resin known in the art, exemplary including but not limited to: any one or a combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac epoxy resin, biphenyl type epoxy resin, alicyclic type epoxy resin or dicyclopentadiene type epoxy resin.
Preferably, the halogen-free epoxidized soybean oil modified resin has a mass of 10 to 45 parts, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts or 44 parts, based on 100 parts of the mass of the epoxy resin, and specific point values between the above point values are not exhaustive for the sake of brevity and conciseness.
In the resin composition provided by the invention, the mass of each component (including epoxy resin, curing agent and halogen-free epoxy soybean oil modified resin) is calculated by the solid content, and the resin composition does not comprise solvent, dispersing agent and the like.
Preferably, the resin composition further comprises any one or a combination of at least two of a curing agent, a curing accelerator, a flame retardant or a filler.
Preferably, the curing agent comprises any one or a combination of at least two of phenolic resin, amine curing agent, cyanate curing agent, active ester curing agent, carboxylic acid curing agent or anhydride curing agent, and further preferably phenolic resin.
Preferably, the curing agent is 20-30 parts by mass, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, based on 100 parts by mass of the epoxy resin, and specific point values among the above point values are limited in scope and are not exhaustive for the sake of brevity.
Preferably, the curing accelerator comprises any one or a combination of at least two of imidazole curing accelerator, organic phosphine curing accelerator, organic amine curing accelerator, peroxide or organic metal salt.
Preferably, the imidazole-based curing accelerator comprises any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole.
Preferably, the curing accelerator is 0.01 to 2 parts by mass based on 100 parts by mass of the epoxy resin, for example, 0.01 part, 0.03 part, 0.05 part, 0.07 part, 0.09 part, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1 part, 1.2 part, 1.5 part or 1.8 part, and specific point values between the above point values are limited in terms of length and size, and the specific point values included in the range are not exhaustive for the sake of brevity.
Preferably, the kind of the flame retardant is not particularly limited, and flame retardants having a flame retardant effect may be used in the resin composition, and exemplary include, but are not limited to: any one or a combination of at least two of an inorganic flame retardant, a phosphorus-based organic flame retardant, a nitrogen-based organic flame retardant and a silicon-containing organic flame retardant.
Preferably, the filler is an organic filler and/or an inorganic filler, the kind of which is not particularly limited, and exemplary include, but are not limited to: any one or a combination of at least two of silica, titania, aluminum hydroxide, magnesium hydroxide, boehmite, talc, mica powder, molybdenum oxide, zinc molybdate, zinc oxide, boron nitride, aluminum nitride, silicon carbide, alumina, barium sulfate, barium titanate, calcium carbonate, glass frit, or short glass fibers.
Preferably, the filler is 20-60 parts by mass, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts, based on 100 parts by mass of the epoxy resin, and specific point values between the above point values are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
The resin composition may further contain a solvent, and the amount of the solvent to be added may be selected by those skilled in the art according to experience and process requirements, so that the resin composition may have a viscosity suitable for use, thereby facilitating impregnation, coating, etc. of the resin composition. The solvent in the resin composition may be partially or completely volatilized during the subsequent drying, semi-curing or complete curing steps.
The solvent of the present invention is not particularly limited, and generally, ketones such as acetone, butanone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, and butanol, alcohols such as ethylcellosolve, butylcellosolve, ethylene glycol monomethyl ether, carbitol, and butylcarbitol, and nitrogen-containing compounds such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; the solvent may be used alone or in combination of two or more. Ketones such as butanone, acetone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferable.
The resin composition provided by the invention is prepared by the following method, and the preparation method comprises the following steps: mixing a main resin (epoxy resin), the halogen-free epoxidized soybean oil modified resin and a curing agent with optional solvents, curing accelerators, fillers and flame retardants, and uniformly dispersing to obtain the resin composition.
In a fourth aspect, the present invention provides a prepreg comprising a reinforcing material and the resin composition according to the third aspect attached to the reinforcing material.
Preferably, the resin composition is attached to the reinforcing material after drying by impregnation.
Preferably, the reinforcing material comprises any one or at least two of natural fibers, organic synthetic fibers, organic fabrics, inorganic fibers or inorganic fabrics; such as fiberglass cloth, quartz glass fiber blend cloth, nonwoven cloth, quartz cloth, paper, etc.
Illustratively, the preparation method of the prepreg comprises the following steps: and infiltrating the reinforcing material with the glue solution of the resin composition, and then drying to obtain the prepreg.
Preferably, the drying temperature is 120-180deg.C, such as 120deg.C, 125deg.C, 130deg.C, 135deg.C, 140deg.C, 145 deg.C, 150deg.C, 155 deg.C, 160deg.C, 165 deg.C, 170deg.C, 175 deg.C, etc.
In a fifth aspect, the invention provides a copper-clad plate, which comprises a copper foil and the prepreg according to the fourth aspect.
Preferably, the copper-clad plate comprises at least one prepreg and copper foils arranged on one side or two sides of the prepreg.
Preferably, the number of prepregs in the copper-clad plate is 1-12, for example, 2, 5, 8, 10 or 12 prepregs may be used.
Illustratively, the method for preparing the copper-clad plate comprises the following steps: pressing copper foil on one side or two sides of a piece of prepreg, and curing to obtain the copper-clad plate; or laminating at least two prepregs on a laminated board, laminating copper foils on one side or two sides of the laminated board, and curing to obtain the copper-clad plate.
Preferably, the curing is performed in a press.
Preferably, the curing temperature is 150-200 ℃, e.g., 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, etc.
Preferably, the curing pressure is 10-30kg/cm 2 For example 10kg/cm 2 、12kg/cm 2 、15kg/cm 2 、17kg/cm 2 、20kg/cm 2 、22kg/cm 2 、25kg/cm 2 、27kg/cm 2 Or 29kg/cm 2 Etc.
Preferably, the curing time is 60-150min, such as 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 145min, etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) The halogen-free epoxy soybean oil modified resin provided by the invention contains a flexible long carbon chain structure and proper branching degree, has good compatibility with main resin, can obviously improve the toughness of a resin cured product, can keep the heat resistance at a high level, does not contain halogen, and meets the green environment-friendly requirement.
(2) The preparation process of the halogen-free epoxidized soybean oil modified resin has mild conditions, is easy to operate, is safe and environment-friendly, adopts renewable materials as raw materials in the preparation process, has wide sources and low cost, is suitable for large-scale industrialized mass production, and is easy to popularize and apply.
(3) The cured product of the resin composition comprising the halogen-free epoxidized soybean oil modified resin has excellent toughness and impact resistance and has a high T g And excellent heat resistance. Copper-clad plate containing the resin composition has strong impactDegree > 102kJ/m 2 The elastic modulus is 16511-19141MPa, has lower modulus, high impact strength and excellent toughness, and has T g The thermal decomposition temperature is higher than 122 ℃, the thermal decomposition temperature is higher than 300 ℃, and the heat resistance is good, so that the resin composition and the copper-clad plate have excellent toughness, impact performance and heat resistance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the following embodiments of the present invention, epoxidized soybean oil is commercially available, for example, from HM-01R, inc. of the Nandina technology Co.
In the following embodiments of the invention, the epoxy equivalent (including intermediates and end products) referred to is determined using an automatic potentiometric titration apparatus, specifically by perchloric acid titration.
Example 1
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-1 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.364:1, adding triphenylphosphine accounting for 0.08% of the total mass of the mixture as a catalyst, heating to 130 ℃ for reaction for 3 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 318g/eq;
(2) Adding 0.313mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 2 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-1, and obtaining the epoxy equivalent of 450g/eq through actual measurement; toluene with the mass accounting for 10% of the total product is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-1.
Example 2
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-2 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.329:1, adding triphenylphosphine accounting for 0.06% of the total mass of the mixture as a catalyst, heating to 160 ℃ for reaction for 1h, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 300g/eq;
(2) Adding 0.232mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 1 hour under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-2, and obtaining the epoxy equivalent of 400g/eq through actual measurement; toluene with the mass accounting for 10% of the total product is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-2.
Example 3
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-3 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.399:1, adding triphenylphosphine accounting for 0.10% of the total mass of the mixture as a catalyst, heating to 140 ℃ for reaction for 2 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 350g/eq;
(2) Adding 0.398mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-3, and obtaining the epoxy equivalent of 500g/eq through actual measurement; toluene with the mass accounting for 10% of the total product is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-3.
Example 4
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-4 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.347:1, adding triphenylphosphine accounting for 0.07% of the total mass of the mixture as a catalyst, heating to 120 ℃ for reaction for 5 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 337g/eq;
(2) Adding 0.353mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-4, and obtaining the epoxy equivalent of 468g/eq through actual measurement; toluene accounting for 10% of the total product mass is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-4.
Example 5
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-5 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil according to a molar ratio of 0.382:1, adding triphenylphosphine accounting for 0.09% of the total mass of the mixture as a catalyst, heating to 150 ℃ for reaction for 4 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 342g/eq;
(2) Adding 0.282mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 2 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-5, and obtaining 433g/eq through actual measurement; toluene with the mass accounting for 10% of the total product is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-5.
Example 6
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-6 comprise epoxidized soybean oil (epoxy value 6.6%), oleic acid and 4,4' -diaminodiphenyl methane; the preparation method comprises the following steps:
(1) Mixing oleic acid and epoxidized soybean oil in a molar ratio of 0.399:1, adding triphenylphosphine accounting for 0.10 percent of the total mass of the mixture as a catalyst, heating to 140 ℃ for reaction for 2 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 342g/eq;
(2) Adding 0.398mol of 4,4' -diaminodiphenyl methane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-6, and obtaining the epoxy equivalent of 495g/eq through actual measurement; toluene accounting for 10% of the total product mass is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-6.
Example 7
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-7 comprise epoxidized soybean oil (epoxy value 6.6%), stearic acid and hexamethylenediamine; the preparation method comprises the following steps:
(1) Mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.364:1, adding triphenylphosphine accounting for 0.08% of the total mass of the mixture as a catalyst, heating to 130 ℃ for reaction for 3 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is 318g/eq;
(2) Adding 0.213mol of hexamethylenediamine into the system of the step (1), reacting for 2 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxidized soybean oil modified resin E-7, and obtaining the epoxy equivalent of 456g/eq through actual measurement; toluene accounting for 10% of the total product mass is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-7.
Comparative preparation example 1
The preparation raw materials of the halogen-free epoxidized soybean oil modified resin E-D1 comprise epoxidized soybean oil (epoxy value 6.6%), 4' -diaminodiphenyl methane and triphenylphosphine; the preparation method comprises the following steps:
(1) Sequentially adding 100g of epoxidized soybean oil, 6.8g of 4,4' -diaminodiphenylmethane and 0.085g of triphenylphosphine into a reactor, heating to 120 ℃ while stirring, and reacting for 60min to obtain a reaction product;
(2) Naturally cooling the reaction product of the step (1) to 80 ℃, carrying out heat preservation reaction for 30min at the temperature, naturally cooling to 60 ℃, carrying out heat preservation reaction for 30min at the temperature, and then cooling to room temperature to obtain halogen-free epoxidized soybean oil modified resin E-D1, wherein the epoxy equivalent is 448g/eq obtained through actual measurement; toluene with the mass accounting for 10% of the total product is added into the system to obtain the glue solution of the halogen-free epoxidized soybean oil modified resin E-D1.
Comparative preparation example 2
The halogen-free epoxidized soybean oil modified resin E-D2 is prepared from the raw materials of epoxidized soybean oil, phenol, bisphenol A, 2-methylimidazole, formaldehyde, an alkaline catalyst, a solvent, graphene and graphene oxide; the preparation method comprises the following steps:
adding 1400 parts of epoxidized soybean oil, 565 parts of phenol and 1100 parts of bisphenol A into a reaction kettle, stirring for 10min, mixing, adding 8 parts of 2-methylimidazole, reacting for 5h at 180 ℃, naturally cooling the temperature in the reaction kettle to 165 ℃, slowly cooling water to 85 ℃, adding 945 parts of formaldehyde, stirring for 10min, adding 80 parts of triethylamine and 27 parts of ammonia water, reacting for 60min at 100 ℃, sampling to measure the gel time, vacuumizing for 1h when the gel time is measured to be 240+/-10 s (160 ℃), stopping vacuumizing after the resin system in the reaction kettle is transparent, sampling again to measure the gel time, and cooling the temperature in the reaction kettle to not higher than 85 ℃ when the gel time is measured to be 130+/-10 s (160 ℃), and adding 30 parts of graphene, 28 parts of a mixture of graphene oxide and methanol to obtain the epoxidized soybean oil modified phenolic resin E-D2.
The materials involved in the following specific embodiments of the invention include:
(1) Epoxy resin: bisphenol a epoxy resin, DER331, available from DOW chemistry;
(2) Curing agent: phenolic novolac resin, PF8063, purchased from san francisco;
(3) Halogen-free epoxy soybean oil modified resin
Halogen-free epoxidized soybean oil modified resin E-1, example 1;
halogen-free epoxidized soybean oil modified resin E-2, example 2;
halogen-free epoxidized soybean oil modified resin E-3, example 3;
halogen-free epoxidized soybean oil modified resin E-4, example 4;
halogen-free epoxidized soybean oil modified resin E-5, example 5;
halogen-free epoxidized soybean oil modified resin E-6, example 6;
halogen-free epoxidized soybean oil modified resin E-7, example 7;
halogen-free epoxy soybean oil modified resin E-D1, comparative preparation example 1;
halogen-free epoxy soybean oil modified phenolic resin E-D2, comparative preparation example 2;
(4) Curing accelerator: 2-ethyl-4-methylimidazole;
(5) And (3) filling: aluminum hydroxide;
(6) Other toughening agents
Epoxidized soybean oil having an epoxy value of 6.6%, HM-01R, nantong sea grape manufacturing company, inc.;
isopropylated triphenyl phosphate (IPPP).
Application example 1
The resin composition comprises the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 22.4 parts of linear phenolic resin, 22 parts of halogen-free epoxy soybean oil modified resin E-1,0.1 part of 2-ethyl-4-methylimidazole and 30 parts of aluminum hydroxide.
A prepreg and a copper-clad plate containing the resin composition are prepared by the following steps:
(1) Mixing the resin composition with butanone according to the formula amount, and uniformly dispersing by using a high-shear dispersing emulsifying machine to prepare glue solution with the solid content of 70%; impregnating the glass fiber cloth with the glue solution, and then drying in an oven at 170 ℃ for 4min to obtain a prepreg;
(2) Laminating 8 prepregs, covering 35 μm copper foil on upper and lower sides, vacuum pressing at 190 deg.C, 30kg/cm 2 And curing for 2 hours to obtain the copper-clad plate.
Application examples 2 to 5, comparative examples 1 to 9
A resin composition, the components and mass of which are shown in tables 1 and 2; the mass units of each component in tables 1 and 2 are parts.
TABLE 1
TABLE 2
The above resin composition was prepared into a copper-clad laminate according to the method in application example 1, and the following performance test was performed thereon:
(1) Impact strength: the method is suitable for testing the impact strength of the laminated board material with specified size and shape. The size of the sample is long: 120mm wide by 10mm; 10 samples are used for each batch, 5 samples are used in the longitudinal direction and 5 samples are used in the transverse direction; and (3) testing by adopting a simple supported beam pendulum impact tester, calculating the impact strength of each sample according to the following formula A, and calculating the average impact strength according to the impact strength of each sample.
In the formula A, a k : impact strength, kJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the A: breaking work consumed by the sample, J; b: sample width or notch width, mm; d: sample thickness or minimum thickness at notch, mm.
(2) Modulus of elasticity: the determination was carried out according to the IPC-TM-650.2.4.4 method.
(3) Glass transition temperature T g : the determination was carried out according to the IPC-TM-650.2.4.25 method.
(4) Thermal decomposition temperature: the determination was carried out according to the IPC-TM-650.2.4.24.6 method.
The test results are shown in table 3:
TABLE 3 Table 3
As can be seen from the test data in Table 3, in the resin compositions and the copper-clad plates provided in application examples 1 to 7, the halogen-free epoxy soybean oil modified resin provided by the invention is adopted as a toughening agent, so that the toughness and impact resistance of an epoxy cured product can be remarkably improved, and the impact strength of the copper-clad plate is 102.2 to 121.5kJ/m 2 The elastic modulus is 16511-19141MPa, the impact strength of the copper-clad plate is obviously improved, the modulus of the plate is effectively reduced, the toughness of the plate is finally improved, the heat resistance of the plate is not greatly influenced, and T is not influenced g The thermal decomposition temperature is 122.6-129.4 ℃ and 300.4-305.6 ℃, and the high heat resistance level is maintained.
The resin compositions of comparative examples 1 to 5 were free of any toughening agent, so that the impact strength of the copper-clad plate was significantly smaller, the elastic modulus was high, and the toughness of the plate was deteriorated. In comparative example 6, isopropyl triphenyl phosphate was used as a toughening agent, and although toughness of the copper-clad plate was improved, glass transition temperature of a cured product was drastically lowered due to plasticization of the material itself, and thermal decomposition temperature was also lowered simultaneously, which had a great negative effect on heat resistance. In the resin composition of comparative example 7, unmodified epoxidized soybean oil is used as a toughening agent, and the material is a short flexible molecular chain segment, so that the toughening effect is limited, the impact toughness and heat resistance of the copper-clad plate prepared from the material are difficult to meet the requirement of further processing, and the compatibility of the unmodified epoxidized soybean oil and matrix epoxy resin is poor, and the unmodified epoxidized soybean oil is easy to separate out in practical application, so that the heat resistance is obviously insufficient. In comparative example 8, the epoxy soybean oil modified resin prepared from polyamine and epoxy soybean oil is used as a toughening agent, and the molecular structure lacks a flexible chain segment, so that the toughening effect is limited, and the impact strength of the copper-clad plate is insufficient. The resin composition of comparative example 9 uses epoxidized soybean oil modified phenolic resin as a toughening agent, and since the modified reaction activity of the epoxidized soybean oil on the phenolic resin is low, the conversion rate of epoxy groups is still low even if the epoxy groups react for a long time under alkaline and high temperature conditions, and therefore the system contains more suspension chains grafted by etherification and blends in a free state, the heat resistance of the resin is poor, and the performances of an epoxy cured product and a copper-clad plate are further affected.
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (22)

1. The halogen-free epoxidized soybean oil modified resin is characterized in that the preparation raw materials of the halogen-free epoxidized soybean oil modified resin comprise epoxidized soybean oil, C12-C20 fatty acid and polyamine;
the polyamine is H 2 N-R-NH 2 R is selected from the group consisting of C1-C10 linear or branched alkylene, C6-C20 arylene,Any one of them;
m 1 、m 2 each independently selected from integers from 0 to 5, and m 1 +m 2 ＞0；
L is selected from any one of-O-, -S-, -SO-, and C1-C10 straight-chain or branched-chain alkylene;
* Represents the attachment site of the group;
the epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the intermediate reacts with polyamine to obtain the halogen-free epoxidized soybean oil modified resin;
the epoxy equivalent of the intermediate is 300-350g/eq, and the epoxy equivalent of the halogen-free epoxidized soybean oil modified resin is 400-500g/eq.
2. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein the C12-C20 fatty acid is a C12-C20 saturated fatty acid and/or a C12-C20 unsaturated fatty acid.
3. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein the C12-C20 fatty acid is any one or a combination of at least two of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid or arachidic acid.
4. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein the molar ratio of epoxidized soybean oil to C12-C20 fatty acid is 1: (0.3-0.4).
5. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein the molar ratio of epoxidized soybean oil to C12-C20 fatty acid is 1: (0.329-0.399).
6. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein R is selected from the group consisting of C2-C8 linear or branched alkylene groups, Any one of the following.
7. The halogen-free epoxidized soybean oil modified resin of claim 1 wherein the polyamine is any one or a combination of at least two of ethylenediamine, hexamethylenediamine, m-phenylenediamine, m-xylylenediamine or diaminodiphenylmethane.
8. A method of preparing the halogen-free epoxidized soybean oil modified resin of any of claims 1 to 7, comprising: the epoxidized soybean oil reacts with C12-C20 fatty acid to obtain an intermediate; and reacting the intermediate with polyamine to obtain the halogen-free epoxy soybean oil modified resin.
9. The method of claim 8, wherein the reaction of the epoxidized soybean oil with the C12-C20 fatty acid is carried out in the presence of a catalyst.
10. The method of claim 9, wherein the catalyst comprises any one or a combination of at least two of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, or 2-phenyl-4-methylimidazole.
11. The preparation method according to claim 9, wherein the mass of the catalyst is 0.01 to 0.2% based on 100% of the total mass of the epoxidized soybean oil and the C12-C20 fatty acid.
12. The method of claim 8, wherein the reaction temperature of the epoxidized soybean oil and the C12-C20 fatty acid is 100-180 ℃.
13. The method of claim 8, wherein the reaction time of the epoxidized soybean oil with the C12-C20 fatty acid is from 0.5 to 8 hours.
14. The process of claim 8, wherein the reaction temperature of the intermediate with the polyamine is 100-180 ℃.
15. The method of claim 8, wherein the reaction time of the intermediate with the polyamine is 0.5 to 5 hours.
16. A resin composition comprising a host resin and the halogen-free epoxidized soybean oil modified resin of any of claims 1 to 7.
17. The resin composition of claim 16, wherein the host resin comprises an epoxy resin.
18. The resin composition according to claim 17, wherein the halogen-free epoxidized soybean oil modified resin has a mass of 10 to 45 parts based on 100 parts by mass of the epoxy resin.
19. The resin composition of claim 16, further comprising any one or a combination of at least two of a curing agent, a curing accelerator, a flame retardant, and a filler.
20. A prepreg comprising a reinforcing material and the resin composition of any one of claims 16-19 attached to the reinforcing material.
21. A prepreg according to claim 20, wherein the resin composition is attached to the reinforcing material after drying by impregnation.
22. A copper-clad plate, characterized in that it comprises a copper foil and the prepreg according to claim 20 or 21.
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