WO2016095870A1 - Bisphenol and diamine containing benzocyclobutene structural unit, and preparation and application thereof - Google Patents

Abstract

Provided are a bisphenol and diamine containing benzocyclobutene structural unit, and preparation and application thereof; specifically, the present invention uses 4-halo-benzocyclobutene as a raw material to obtain 4-acyl-benzocyclobutene via acylation, and the 4-acyl-benzocyclobutene is reacted with substituted phenol or aniline in an acidic condition to obtain a compound represented by formula I, definitions of each group are described in the specification. The process of the present invention is simple, can be operated easily, has an excellent yield, and is suitable for large-scale industrial production; and the obtained product has a curable group, and can be used to prepare a novel organic thermoset material having high-performance.

Description

Bisphenol and bisamine containing benzocyclobutene structural unit and preparation and application thereof Technical field

The invention belongs to the field of manufacturing high performance polymer intermediates, and in particular relates to a method for producing bisphenols and bisamines containing benzocyclobutene structural units and applications thereof.

Background technique

Bisphenols and diamines are two important organic chemical raw materials and are widely used. At present, bisphenols or diamines commonly found in the art are: bisphenol A, bisphenol F, bisphenol S, hexafluorobisphenol A, 4,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, etc.:

Bisphenol compounds can be used to produce a variety of polymer materials such as polycarbonate, epoxy resin, polyester resin, polysulfone resin, polyphenylene ether resin, etc., while bisamine compounds are used in epoxy resin curing agents, polyamides. There are important applications in the fields of amines, polyurethanes, polycarbonates, polysulfone resins, and phenolic unsaturated resins. Commonly used bisphenols, bisamines such as bisphenol A, 4,4'-diaminodiphenyl ether, etc., have only two functionalities, and the usually formed polymer is a chain polymer, and the properties of the obtained material are closely related to the molecular weight. It is a thermoplastic material. However, thermoplastic materials are generally poor in high temperature resistance and rigidity. Although the polyimide has excellent comprehensive properties, it has been widely used in aerospace, microelectronics, high temperature resistant films, etc., but with the advancement of technology, higher Performance materials also show urgent demand, and one of the major areas is the development of polyimides with superior performance.

Generally speaking, increasing the molecular weight is a common means to improve the performance of the polymer. However, as the molecular weight increases, the solubility and processability of the polymer may decrease. In general, the polymerization is not affected. Under the premise of solubility and processability, by introducing a curable group, the polymer is formed into a network structure by curing cross-linking, which is a common method for improving the material properties. Taking polyimide as an example, by introducing a curable capping group, it is a common means to improve its performance. The types reported have mainly been norbornene-terminated (J. App. Poly. Sci. 1972, 16, 905.) and other alkenyl-containing fragment-terminated, acetylene-containing end-capped types (Macromolecules, 2003, 36, 6780). .), maleimide terminated type (Polymer) 1996, 37, 5077.), cyano and other carbon-nitrogen-free unsaturated end-capped (Polymer 2009, 50, 1700.), epoxy terminated and trialkoxysilane terminated (Polym. Prepr.1986 , 27, 403.) type and so on.

Benzocyclobutene is a thermosetting group with high reactivity and no small molecule release when cured. It has a low curing temperature, good processability and film forming properties, and a lighter cured product with a lower dielectric constant. And high thermal stability has attracted much attention. If benzocyclobutene can be introduced into a small molecule, a new small molecule can be synthesized to become part of the main chain, or the polymer can be introduced by copolymerization or doping to enhance the polymerization in a controlled manner. The performance of the object. However, the cyclobutene structural unit in the benzocyclobutene is very easy to open and thus is difficult to introduce into the polymerization monomer.

In summary, there is an urgent need in the art for a method for efficiently introducing a benzocyclobutene structural unit into a bisphenol or a diamine compound to prepare a polymerized monomer.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for efficiently preparing a benzocyclobutene structural unit into a bisphenol or a diamine compound to prepare a polymerizable monomer.

In a first aspect of the invention, there is provided a class of compounds having the structure of formula I:

In the formula,

Each R is independently selected from the group consisting of -OH, -NH ₂ ;

Each R _{1 is} independently selected from the group consisting of H, C1-C4 alkyl;

R _{2 is} selected from the group consisting of H, a C1-C4 alkyl group, and a C1-C4 haloalkyl group (preferably a fluoroalkyl group).

In another preferred embodiment, the compound of formula I is prepared by a process comprising the steps of:

(ii) acylation with a compound of formula III (4-halobenzocyclobutene) in a polar solvent to provide a compound of formula II;

(i) reacting with a compound of formula II in a polar solvent to provide a compound of formula I;

Wherein X is selected from the group consisting of halogen; the remaining groups are as defined in the first aspect of the invention.

In another preferred embodiment, each of said R ₁ is the same.

In another preferred embodiment, each of said R is the same.

In another preferred embodiment, each of said R is independently selected from the group consisting of -OH, -NH ₂ ;

Each R _{1 is} independently selected from the group consisting of H, —CH ₃ ;

R _{2 is} selected from the group consisting of H, -CH ₃ , and -CF ₃ .

According to a second aspect of the invention, there is provided a process for the preparation of a compound I according to the first aspect of the invention, the method comprising the steps of:

(i) reacting a compound of formula II with a compound of formula IV or a salt thereof with an acid in an inert solvent to provide a compound of formula I;

Wherein each group is as defined in the first aspect of the invention; preferably, in the step (i), the molar ratio of the compound of the formula II to the compound of the formula IV is from 1:1.5 to 5, preferably 1 : 2.5 to 3.

In another preferred embodiment, the step (i) is carried out in the presence of an acid catalyst; preferably, in the step, the ratio of the compound of the formula II to the acid is 1:0.1 to 1.

In another preferred embodiment, in the step (i), the inert solvent is a polar solvent; preferably, the polar solvent is selected from the group consisting of CH ₂ Cl ₂ , CHCl ₃ , ClCH ₂ CH ₂ Cl, toluene, or a combination thereof.

In another preferred embodiment, in the step (i), the inert solvent is aniline. In another preferred embodiment, in the step, the temperature of the reaction is from 0 to 180 °C.

In another preferred embodiment, in the step, the reaction time is 24 to 72 hours.

In another preferred embodiment, the salt of the compound of formula IV with an acid is a protonate salt of a compound of formula IV.

In another preferred embodiment, when each R is -OH, the method includes the steps of:

(ia) reacting a compound of formula II with a compound of formula IV in a polar solvent to provide a compound of formula I, and said step (ia) is carried out in the presence of an acid; preferably, said acid is a protic acid, more Preferably, it is selected from the group consisting of HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or a combination thereof.

In another preferred embodiment, in the step (ia), the ratio of the compound of the formula II to the acid is 1:0.1 to 1.

In another preferred embodiment, in the step (ia), the ratio of the compound of the formula II to the substituted phenol is 1:1.5 to 5, preferably, the ratio is 1:2.5 to 3.

In another preferred embodiment, in the step (ia), the solvent is a polar solvent; preferably, the polar solvent is selected from the group consisting of CH ₂ Cl ₂ , CHCl ₃ , ClCH ₂ CH ₂ Cl, toluene, or a combination thereof.

In another preferred embodiment, in the step (ia), the temperature of the reaction is from 0 to 80 °C.

In another preferred embodiment, in the step (ia), the reaction time is from 24 to 72 hours.

In another preferred embodiment, when each R is -NH ₂ , the method comprises the steps of:

(ib) reacting a compound of formula II with a compound of formula IV or a salt thereof with an acid in a polar solvent to provide a compound of formula I;

Preferably, the step (ib) is carried out in the presence of an acid; preferably, the acid is selected from the group consisting of HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or Its combination.

In another preferred embodiment, in the step (ib), the ratio of the compound of the formula II to the acid is 1:0.1 to 1.

In another preferred embodiment, in the step (ib), the solvent is a compound of the formula IV (ie, the corresponding reactant aniline).

In another preferred embodiment, in the step (ib), the temperature of the reaction is from 100 to 180 °C.

In another preferred embodiment, in the step (ib), the reaction time is from 24 to 72 hours.

In another preferred embodiment, when the reactant is a compound of formula II and a compound of formula IV, said step (ib) is carried out in the presence of an acid.

In another preferred embodiment, when the reactant is a salt of a compound of formula II with a compound of formula IV and an acid, said step (ib) is carried out in the absence of an acid.

In another preferred embodiment, the method further includes the steps of:

(ii) reacting a compound of formula III (4-halobenzocyclobutene) with an acylating reagent in a polar solvent to provide a compound of formula II;

Wherein X is selected from the group consisting of halogen; the remaining groups are as defined in the first aspect of the invention.

In another preferred embodiment, said R _{2 is} selected from the group consisting of H, -CH ₃ , -CF ₃ .

In another preferred embodiment, said X is selected from the group consisting of Cl, Br.

In another preferred embodiment, in the step (ii), the solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methylcyclohexyl ether, or a combination thereof.

In another preferred embodiment, in the step (ii), the ratio of the prepared aryl anion to the acylating agent is 1:1 to 1.5.

In another preferred embodiment, in the step (ii), the temperature of the reaction is -78 to 30 °C.

In another preferred embodiment, in the step (ii), the reaction time is from 1 to 10 hours.

In another preferred embodiment, the step (ii) further comprises: preparing an aryl anion by using a 4-halobenzocyclobutene in a polar solvent, and then reacting with an acylating reagent to obtain a compound of the formula II; Preferably, in the step (ii), the method for preparing an aryl anion by using a 4-halobenzocyclobutene is selected from the group consisting of:

(1) Lithium halide exchange with a compound of the formula III and an alkyllithium reagent (preferably n-butyllithium) to obtain an aryllithium salt; preferably, when the aryl anion is prepared by the method (1), X is Br; or

(2) reacting a compound of the formula III with magnesium metal to obtain an aryl Grignard reagent; preferably, when the aryl anion is prepared by the method (2), the X is Cl or Br.

In another preferred embodiment, in the method (1), the method is carried out at a low temperature (preferably -78 ° C to -30 ° C).

其中，R₂的定义如本发明第一方面中所述；R选自下组：-N(R’)₂、-OR’，其中，所述的R’为C1-C4的烷基。In another preferred embodiment, in the step (ii), the acylating reagent is

Wherein R _{2 is} as defined in the first aspect of the invention; R is selected from the group consisting of -N(R') ₂ , -OR', wherein said R' is a C1-C4 alkyl group.

In another preferred embodiment, the acylating agent is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, Ethyl trifluoroacetate, methyl trifluoroacetate.

In another preferred embodiment, when R ₂ is H, the acylating agent is N,N-dimethylformamide.

In another preferred embodiment, when R ₂ is CH ₃ , the acylating agent is selected from the group consisting of N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, or combination.

In another preferred embodiment, when R ₂ is CF ₃ , the acylating agent is selected from the group consisting of ethyl trifluoroacetate, methyl trifluoroacetate, or a combination thereof.

In a third aspect of the invention, there is provided a compound of formula II:

Wherein R _{2 is} selected from the group consisting of C1-C4 haloalkyl (preferably fluoroalkyl).

According to a fourth aspect of the invention, there is provided a use of a compound I according to the first aspect of the invention, for:

(a) preparing a thermosetting material;

(b) modifying existing products or preparing new materials as additives to bisphenol or bisamine products;

(c) for the preparation of a polymer intermediate.

According to a fifth aspect of the invention, there is provided an article comprising the compound I according to the first aspect of the invention as an additive; preferably, the article is an epoxy resin article.

According to a sixth aspect of the invention, there is provided a polymer prepared by homopolymerization or copolymerization of the compound I according to the first aspect of the invention as a monomer; preferably, the polymerization The substance has a structure selected from the group consisting of:

In another preferred embodiment, the polymer is selected from the group consisting of polyesters, polyethers, polyetheretherketones, polyimides, polyurethanes, polyisocyanates, polyarylates, or polycarbonates.

Blending the compound I of the first aspect of the invention as an additive with an existing article can improve the properties of the existing article; preferably, the existing article is an epoxy resin.

It is to be understood that within the scope of the present invention, the various technical features of the present invention and the various technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here.

Detailed ways

The inventors have prepared a novel bisphenol and bisamine containing a benzocyclobutene structural unit through long-term and intensive research. The bisphenol and bisamine contain a curable group, which can be converted into a thermosetting material after being used as a main raw material or an additive. Moreover, the above method has simple reaction steps and high yield, and is very suitable for industrial production. The bisphenol and bisamine can replace the existing industrial raw materials bisphenol, bisamine, or co-polymerization with existing bisphenols and bisamines to prepare novel thermosetting materials, thereby preparing cured products with special properties. Based on the above findings, the inventors completed the present invention.

the term

As used herein, the term "bisphenol" refers to a compound containing two phenolic hydroxyl groups, such as the commonly used commercial industrial materials bisphenol A, bisphenol F, bisphenol S, hexafluorobisphenol A, and the like. In particular, a preferred class of bisphenols are the bisphenols containing benzocyclobutene structural units provided by the present invention.

The term "diamine" refers to a compound having two aminophenyl groups, such as the commonly used commercial industrial materials 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl sulfone and the like. In particular, a preferred class of bisamines are the bisamines containing benzocyclobutene structural units provided by the present invention.

The term "halogen" means fluoro, chloro, bromo, iodo.

The term "halo" means that one or more hydrogen atoms on the group are replaced by a halogen.

The term "C1-C6 alkyl" refers to a straight or branched alkyl group having from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or Similar group.

Bisphenol or bisamine containing a benzocyclobutene structural unit

Considering the simple route and simple method in industrialization, the inventors designed a new class of bisphenols and diamines containing benzocyclobutene structural units, which are used as existing commercial bisphenols and diamines. The substitute or the additive is added to a product containing a commercial bisphenol or a diamine, and is cured by heat curing to obtain a novel material which is more excellent in performance.

The bisphenol or bisamine containing a benzocyclobutene structural unit provided by the present invention has a structure represented by the following formula I:

In the formula,

Each R is independently selected from the group consisting of -OH, -NH ₂ ;

Each R _{1 is} independently selected from the group consisting of H, C1-C4 alkyl;

R _{2 is} selected from the group consisting of H, a C1-C4 alkyl group, and a C1-C4 haloalkyl group (preferably a fluoroalkyl group).

In the above monomers, each R or R ₁ may be the same or different, preferably, each of the R ₁ is the same; and/or each of the R is the same. In a most preferred configuration, each R ₁ and each R are the same.

In a preferred class of embodiments of the invention, each R is independently selected from the group consisting of -OH, -NH ₂ ; each R _{1 is} independently selected from the group consisting of H, -CH ₃ ; _{2 is} selected from the group consisting of H, -CH ₃ , and -CF ₃ .

The bisphenol or bisamine can be used in place of the existing bisphenol or bisamine for the preparation of existing polymers using bisphenol or bisamine as monomers, such as polyester, polyether, polyetheretherketone. , polyimide, polyurethane, polyisocyanate, and the like. Preferred polymers are practiced, for example, as polyaramidates, or as polycarbonates.

Preparation of bisphenol or bisamine containing benzocyclobutene structural unit

The present invention also provides a process for the preparation of a class of the above-mentioned compound I, which comprises 4-halobenzocyclobutene as a raw material, which is subjected to an acylation reaction to obtain a 4-acyl substituted benzocyclobutene, the latter The benzocyclobutene-modified bisphenol and bisamine monomer are obtained by reacting with a substituted phenol or an aniline under acidic conditions. The method has short reaction route and high yield, and is suitable for industrial production.

Specifically, the method includes the steps of:

(i) reacting a compound of formula II with a compound of formula IV in an inert solvent to provide a compound of formula I;

Wherein each group is as defined above.

In the above reaction, the ratio of each raw material is not particularly limited. Preferably, in the step (i), the molar ratio of the compound of the formula II to the compound of the formula IV is 1:1.5 to 5, preferably 1:2.5 to 3. .

In another preferred embodiment, the step (i) is carried out in the presence of an acid; in particular, since the cyclobutene structural unit is extremely susceptible to ring opening, the acid preferably should have a moderate acidity so that This reaction can be carried out without opening the cyclobutene structural unit. After screening, the inventors found that protonic acids (such as HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, etc.) have little effect on the benzocyclobutene structural unit in the reaction, and the reaction process It does not cause benzocyclobutene ring opening (maintaining stability up to 150 ° C), while Lewis acids (such as ZnCl ₂ , Al(OPh) _{3 ,} etc.) cause benzocyclobutene at higher temperatures. The open loop of the structural unit results in a lower product yield. For the different reactants, the corresponding most suitable acid can be selected. Preferably, in the step, the molar ratio of the compound of the formula II to the acid is 1:0.1 to 1.

The inert solvent in the step (i) is not particularly limited, and is preferably a polar solvent or an aniline solvent. In a preferred embodiment of the invention, the polar solvent is selected from the group consisting of CH ₂ Cl ₂ , CHCl ₃ , ClCH ₂ CH ₂ Cl, toluene, or a combination thereof.

The temperature of the hydrolysis polymerization is not particularly limited, and it is preferably carried out at 0 to 180 ° C (for example, 20 to 160 ° C). Preferably, the reaction temperature can be optimized depending on the reactants, and such optimization can be made by those skilled in the art in conjunction with the prior art.

The hydrolysis polymerization reaction time is not particularly limited, and the end point of the reaction can be determined by a method generally used in the art (e.g., TLC, etc.). Preferably, the reaction time is 24 to 72 hours.

One skilled in the art can optimize the preferred reaction conditions for the different starting materials in conjunction with the prior art in the art. Such changes will be apparent to those skilled in the art after the structure of the compound of Formula I and the above described preparation methods are disclosed. .

In some preferred embodiments of the invention, when each R is -OH, the method comprises the steps of: (ia) reacting a compound of formula II with a compound of formula IV in a polar solvent to provide a compound of formula I, The step (ia) is carried out in the presence of an acid; preferably, the acid is an acid selected from the group consisting of HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or combination.

In the step (ia), the ratio of the compound of the formula II to the acid is preferably 1:0.1 to 1.

The ratio of each raw material is not particularly limited. Preferably, in the step (ia), the ratio of the compound of the formula II to the substituted phenol is 1:1.5 to 5, preferably, the ratio is 1:2.5 to 3.

The solvent in the step (ia) is preferably a polar solvent; preferably, the polar solvent is selected from the group consisting of CH ₂ Cl ₂ , CHCl ₃ , ClCH ₂ CH ₂ Cl, toluene, or a combination thereof.

In the step (ia), the temperature of the reaction is preferably 0 to 80 ° C (for example, 10 to 40 ° C, or at room temperature). In another preferred embodiment, in the step (ia), the reaction time is from 24 to 72 hours.

In other preferred embodiments of the present invention, when each R are -NH _2, the method comprising the steps of:

(ib) reacting a compound of formula II with a compound of formula IV in a polar solvent to provide a compound of formula I, and said step (ib) is carried out in the presence of an acid; preferably, said acid is selected from the group consisting of: HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or a combination thereof.

In the step (ib), the ratio of the compound of the formula II to the acid is preferably 1:0.1 to 1.

A preferred solvent in one of the steps (ib) is a compound of formula IV, the corresponding reactant aniline. In the reaction, the compound of the formula II can be directly dissolved in the corresponding compound of the formula IV without adding a solvent, and then the reaction can be carried out by adding a suitable acid.

In the step (ib), the temperature of the reaction is preferably from 100 to 180 ° C (for example, from 120 to 160 ° C). In another preferred embodiment, in the step (ib), the reaction time is from 24 to 72 hours.

The bisphenol and bisamine containing a benzocyclobutene structural unit can be used as an existing commercial bisphenol and bisamine substitute to prepare a high performance thermosetting material; and can be used as an additive to be added to a commercial bisphenol. In the diamine product, the existing product is modified or a new material is prepared; and it can be used as a raw material for preparing a novel polymer intermediate.

Preparation of compound of formula II

The invention also provides a process for the preparation of a compound of formula I, intermediate compound II, which employs an acylation reaction to introduce an acyl group into the benzocyclobutene structure, the process comprising the steps of:

(ii) reacting a compound of formula III (4-halobenzocyclobutene) with an acylating reagent in a polar solvent to provide a compound of formula II;

Wherein X is selected from the group consisting of halogen; the remaining groups are as defined above.

In another preferred embodiment, said R _{2 is} selected from the group consisting of H, -CH ₃ , -CF ₃ .

In another preferred embodiment, said X is selected from the group consisting of Cl, Br.

The acylating agent may be an acylating agent commonly used in the art, such as a corresponding acid chloride, acid anhydride, amide, etc., preferably an agent having the following structure:

其中，R₂的定义如本发明第一方面中所述，R选自下组：-N(R’)₂、-OR’，其中，所述的R’为C1-C4的烷基。在另一优选例中，所述的酰化试剂选自下组：N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙酸乙酯、乙酸丙酯、乙酸甲酯、三氟乙酸乙酯、三氟乙酸甲酯。

Wherein R _{2 is} as defined in the first aspect of the invention, and R is selected from the group consisting of -N(R') ₂ , -OR', wherein said R' is a C1-C4 alkyl group. In another preferred embodiment, the acylating agent is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, Ethyl trifluoroacetate, methyl trifluoroacetate.

In the present invention, a suitable acylating agent can be selected depending on the desired structure of the compound of formula II. For example, in a preferred embodiment of the present invention, when R ₂ is H, the acylating agent is preferably N,N-dimethylformamide; when R ₂ is CH ₃ , the acylating agent is preferably Is a reagent selected from the group consisting of N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, or a combination thereof; when R ₂ is CF ₃ , the acylating agent is preferably A reagent selected from the group consisting of ethyl trifluoroacetate, methyl trifluoroacetate, or a combination thereof.

In the step (ii), the solvent is not particularly limited, and is preferably a solvent selected from the group consisting of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methylcyclohexyl ether, or a combination thereof.

In the step (ii), the ratio of each reactant is not particularly limited, and preferably, the ratio of the compound of the formula III to the acylating agent is 1:1 to 1.5.

In the step (ii), the temperature of the reaction is preferably carried out at a lower temperature, and in a preferred embodiment of the invention, the reaction temperature is -100 to 40 °C.

In the step (ii), the reaction time is not particularly limited, and the end point of the reaction can be determined by a method generally used in the art (such as TLC, etc.), and preferably, the reaction time is 1 to 10 hours.

In the present invention, the preferred step (ii) comprises: reacting a 4-halobenzocyclobutene with a base in a polar solvent to obtain an aryl anion, and then reacting with an acylating reagent to obtain a compound of formula II. The method for preparing an aryl anion using 4-halobenzocyclobutene is preferably selected from the group consisting of:

(1) Lithium halide exchange with a compound of the formula III and n-butyllithium to obtain an aryllithium salt; preferably, when the aryl anion is prepared by the method (1), the X is Br;

(2) reacting a compound of the formula III with magnesium metal to obtain an aryl Grignard reagent; preferably, when the aryl anion is prepared by the method (2), the X is Cl or Br.

In another preferred embodiment, in the method (1), the method is carried out at a low temperature (-78 ° C to -30 ° C). In a preferred embodiment of the invention, the method (1) is carried out at -78 ± 5 °C.

In another preferred embodiment, in the method (2), the method is carried out at room temperature, and in particular, the reaction does not affect the benzocyclobutene group.

The main advantages of the present invention over the prior art include:

(1) The method of the invention introduces a curable group into a side chain of bisphenol and a bisamine by a simple method, has simple operation, excellent yield, and does not use a catalyst such as a precious metal, and creates favorable conditions for large-scale industrial production.

(2) The method of the invention structurally modifies the commonly used and excellent bisphenol and bisamine raw materials, so that it can be used for temperature-raising curing, and the material can be greatly improved by crosslinking of benzocyclobutene. The heat resistance and rigidity; at the same time, there is no influence on the performance of the above raw materials at normal temperature.

(3) The method of the invention can be used for preparing novel bisphenol and bisamine polymer monomers containing benzocyclobutene units, which greatly enriches the types of bisphenol and bisamine polymer monomer compounds. It is of great significance for the development of high-performance materials, and it also provides a new idea for the development of high-performance materials monomer compounds.

(4) The method of the invention has simple process, simple operation, excellent yield and is suitable for large-scale industrial production. The obtained product has a curable group, such as replacing it with an existing commercial bisphenol, a diamine raw material or adding it into an existing bisphenol or bisamine product by copolymerization, doping or the like, and converting the thermoplastic material into Thermosetting materials, which in turn improve the heat and solvent resistance of materials, are important for the development of new high performance organic materials.

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

Example 1 Preparation of 4-acetylbenzocyclobutene

To a solution of 4-bromobenzocyclobutene (10 g) in THF (150 mL), a hexane solution (2.5 M, 26 mL) was slowly added dropwise at -78 ° C, and stirred at -78 ° C for 30 min. The DMAc (6.66 g) was slowly added dropwise, and the mixture was stirred slowly to room temperature and then stirred for 4 h, then a saturated NaHCO ₃ solution (100 mL) was added and the mixture was evaporated to ethyl acetate (100 mL x 3), and the organic phase was washed with a saturated sodium chloride solution. dried over anhydrous MgSO _4, rotary evaporation, column chromatography, petroleum ether / ethyl acetate mixture as an eluent to give a white solid 5.92 g, yield 74%.

Nuclear magnetic characterization ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.71 - 7.52 (m, 1H), 7.43 - 7.30 (m, 1H), 6.95 - 6.84 (m, 1H), 2.97 (s, 4H), 2.33 ( s,3H); ¹³ C NMR (126MHz, CDCl ₃ ): δ 197.21, 151.28, 145.39, 135.78, 127.18, 121.90, 121.76, 29.33, 28.87, 25.95 ppm; HRMS (m/z): [M] ⁺ calcd for 146.0732 , found 146.0730.

Example 2 Preparation of 4-acetylbenzocyclobutene

To a 250 mL flask, Mg (2.6 g), THF (100 mL) was successively added at room temperature, and then one iodine was added thereto. In the dropping funnel, 4-bromobenzocyclobutene (10 g) and THF (20 mL) were added, and 5 mL of 4-bromobenzocyclobutene solution was added dropwise to the flask, followed by heating with a hair dryer to initiate the reaction, and the color of the iodine was After disappearing, the dropping rate was controlled, and the reactant was slowly dropped into the flask. After the completion of the dropwise addition, the reaction was carried out for 30 min, and DMAc (6.57 g) was slowly added dropwise thereto. After reacting for 4 hours, a saturated NaHCO ₃ solution (100 mL) was added thereto, and ethyl acetate B was added. ester was extracted (100mL x 3), saturated sodium chloride solution, the organic phase was dried over anhydrous MgSO _4, rotary evaporation, column chromatography, petroleum ether / ethyl acetate mixture as an eluent to give a white solid 5.73g, yield 72 %.

Nuclear magnetic characterization ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.71 - 7.52 (m, 1H), 7.43 - 7.30 (m, 1H), 6.95 - 6.84 (m, 1H), 2.97 (s, 4H), 2.33 ( s,3H); ¹³ C NMR (126MHz, CDCl ₃ ): δ 197.21, 151.28, 145.39, 135.78, 127.18, 121.90, 121.76, 29.33, 28.87, 25.95 ppm; HRMS (m/z): [M] ⁺ calcd for 146.0732 , found 146.0730.

Example 3 Preparation of 4-Trifluoroacetylbenzocyclobutene

The same procedure as in Example 1 or Example 2 was employed, except that DMAc was replaced with ethyl trifluoroacetate to give 4-trifluoroacetylbenzocyclobutene, a colorless liquid. Yield, 76%.

Nuclear Magnetic Characterization ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.97 (d, J = 7.8 Hz, 1H), 7.73 (s, 1H), 7.22 (d, J = 7.9 Hz, 1H), 3.27 (s, 4H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 180.44 (q, J = 34.26 Hz), 155.27, 146.68, 129.71, 128.91, 123.73, 123.13, 117.00 (q, J = 291.67 Hz), 30.13, 29.32; ¹⁹ F NMR (376 MHz, CDCl ₃ ): δ - 70.93. HRMS (m/z): [M] ⁺ calcd for 200.0449, found 200.0448.

Example 4 Preparation of Trifluoromethylbenzocyclobutene bisphenol

CHCl solution of 4-trifluoroacetyl-phenyl benzocyclobutene (400 mg of) was added phenol (500mg) ₃ (4mL) solution, to which was added dropwise _{CF 3 SO 3 H (0.1mL)} , stirred at rt overnight after filtration the filtrate was removed, residue was washed with CHCl _3, and then subjected to column chromatography, eluting with petroleum ether / ethyl acetate to give 530 mg of a white solid, yield 72%.

NMR Characterization _{^{1 H NMR (500MHz, CD 3}} OD): δ6.93 (d, J = 8.7Hz, 5H), 6.83 (d, J = 7.9Hz, 1H), 6.80 (s, 1H), 6.70 (d, J = 8.9 Hz, 4H), 4.90 (s, 2H), 3.03 (dd, J = 15.7, 4.3 Hz, 4H); ¹³ C NMR (126 MHz, CD ₃ OD): δ 157.57, 146.33, 146.11, 140.97, 133.07, 132.30, 129.85, 129.80 (q, J = 285.92 Hz), 125.12, 122.87, 115.63, 65.57 (q, J = 23.48 Hz), 30.10, 29.92; ¹⁹ F NMR (376 MHz, acetate): δ-59.06.HRMS (m) /z):[M] ⁺ calcd for 370.1181, found 370.1179.

Example 5 Preparation of Methylbenzocyclobutene Bisphenol

Methylbenzocyclobutene bisphenol was obtained in the same manner as in Example 4 as a white solid.

Nuclear Magnetic Characterization ¹ H NMR (400 MHz, CD ₃ OD): δ 6.92 - 6.79 (m, 6H), 6.71 (s, 1H), 6.68 - 6.61 (m, 4H), 4.86 (s, 2H), 3.08 (m) , 4H), 2.03 (s, 3H); ¹³ C NMR (126 MHz, CD ₃ OD): δ 156.31, 150.45, 146.07, 144.10, 142.41, 130.93, 128.63, 124.03, 122.55, 115.43, 52.71, 31.74, 30.11, 29.85. HRMS (m/z): [M] ⁺ calcd for 316.1463, found 316.1458.

Example 6 Preparation of Trifluoromethylbenzocyclobutene Diamine

To a solution of 4-trifluoroacetylbenzocyclobutene (400 mg) in aniline (4 mL) at room temperature, CF ₃ SO ₃ H (0.1 mL) was added with stirring, and reacted at 140 ° C for 48 h, then directly subjected to column chromatography, petroleum Elution with ether/ethyl acetate afforded 612 mg (yield:

Nuclear magnetic characterization ¹ H NMR (500 MHz, CD ₃ OD): δ 6.94 (d, J = 7.9 Hz, 1H), 6.89 (d, J = 7.9 Hz, 1H), 6.85 - 6.79 (m, 4H), 6.61 ( d, J = 8.7 Hz, 3H), 4.85 (s, 4H), 3.14 - 3.06 (m, 3H). ¹³ C NMR (126 MHz, CD ₃ OD): δ 146.53, 144.81, 144.55, 140.00, 130.46, 130.10, 128.58 (q, J=286.07), 128.54, 123.78, 121.29, 114.21, 64.13 (q, 22.95), 28.65, 28.49; ¹⁹ F NMR (376 MHz, acetate): δ-59.02; HRMS (m/z): [M] ⁺ calcd for 368.1500, found 368.1501.

Example 7 Preparation of Methylbenzocyclobutene Diamine

Methylbenzocyclobutene bisamine was obtained in the same manner as in Example 6 as a yellow solid.

Nuclear magnetic characterization ¹ H NMR (400 MHz, CD ₃ OD): δ 6.88 (d, J = 7.8 Hz, 1H), 6.84 (d, J = 7.8 Hz, 1H), 6.80 (d, J = 8.5 Hz, 4H) , 6.61 (s, 1H), 6.61 (d, J = 8.5 Hz, 4H), 4.86 (s, 4H), 3.09 (m, 4H), 2.00 (s, 3H); ¹³ C NMR (126 MHz, CD ₃ OD ): δ 150.64, 145.93, 145.92, 143.90, 141.47, 130.57, 128.61, 124.06, 122.48, 116.14, 52.60, 31.61, 30.11, 29.86. HRMS (m/z): [M]+calcd for 314.1783, found 314.1788.

Example 7 Preparation of Trifluoromethylbenzocyclobutene Diamine

Using the same method as in Example 6, except that trifluoromethanesulfonic acid was replaced with aniline hydrochloride, trifluoromethyl was obtained. Benzocyclobutene bisamine.

Nuclear magnetic characterization ¹ H NMR (500 MHz, CD ₃ OD): δ 6.94 (d, J = 7.9 Hz, 1H), 6.89 (d, J = 7.9 Hz, 1H), 6.85 - 6.79 (m, 4H), 6.61 ( d, J = 8.7 Hz, 3H), 4.85 (s, 4H), 3.14 - 3.06 (m, 3H). ¹³ C NMR (126 MHz, CD ₃ OD): δ 146.53, 144.81, 144.55, 140.00, 130.46, 130.10, 128.58 (q, J=286.07), 128.54, 123.78, 121.29, 114.21, 64.13 (q, 22.95), 28.65, 28.49; ¹⁹ F NMR (376 MHz, acetate): δ-59.02; HRMS (m/z): [M] ⁺ calcd for 368.1500, found 368.1501.

Example 8 Preparation of Trifluoromethylbenzocyclobutene Diamine

The same procedure as in Example 6 was carried out except that trifluoromethanesulfonic acid was replaced with aniline sulfate to obtain trifluoromethylbenzocyclobutenediamine.

Nuclear magnetic characterization ¹ H NMR (500 MHz, CD ₃ OD): δ 6.94 (d, J = 7.9 Hz, 1H), 6.89 (d, J = 7.9 Hz, 1H), 6.85 - 6.79 (m, 4H), 6.61 ( d, J = 8.7 Hz, 3H), 4.85 (s, 4H), 3.14 - 3.06 (m, 3H). ¹³ C NMR (126 MHz, CD ₃ OD): δ 146.53, 144.81, 144.55, 140.00, 130.46, 130.10, 128.58 (q, J=286.07), 128.54, 123.78, 121.29, 114.21, 64.13 (q, 22.95), 28.65, 28.49; ¹⁹ F NMR (376 MHz, acetate): δ-59.02; HRMS (m/z): [M] ⁺ calcd for 368.1500, found 368.1501.

Example 9 Preparation of polyarylate containing benzocyclobutene structure

Trifluoromethyl benzocyclobutene the bisphenol (412 mg) and terephthaloyl chloride (226 mg) under ice-bath CH ₂ Cl ₂ (3mL) was slowly added dropwise Et ₃ N (1.5mL), dropwise the ice bath was removed after completed addition, the reaction 2d, to which was added _{H 2 O (100mL), CH} 2 Cl 2 and extracted (50mL x 3), the organic phase was dried over anhydrous MgSO _4, solvent was removed by rotary evaporation was dissolved in a small amount (2mL ) in CH ₂ Cl _2, in MeOH (100 mL) sedimentation, filtered off with suction, washed with anhydrous MeOH, residue redissolved in CH ₂ Cl _2, the settling and again filtered off with suction after 80 deg.] C and dried in vacuo to give a white solid 512mg 8h The yield was 92%.

Nuclear magnetic characterization ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.33 (d, J = 3.7 Hz, 4H), 7.31 - 7.16 (m, 8H), 7.01 (q, J = 8.3 Hz, 2H), 6.87 (s, 1H), 3.18 (d, J = 2.0 Hz, 4H). ¹³ C NMR (126MHz, CDCl ₃ ): δ 164.02, 150.15, 145.79, 145.74, 138.32, 138.23, 133.87, 131.35, 130.39, 128.76, 124.15, 122.43, 121.19 , 64.98 (q, J = 23.48 Hz), 29.65, 29.47; ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ - 58.37.

Compared with the conventional polyarylate polymer, the polymer prepared above has better heat resistance and electrical properties.

Example 10 Preparation of Polycarbonate Containing Benzocyclobutene Structure

Under ice-cooling to a bisphenol-trifluoromethyl-benzocyclobutene (402mg) in Et was slowly added dropwise triphosgene ₃ N (1.5mL) (145mg) in (3mL) solution of CH ₂ Cl _2, the addition was complete ice bath was removed, the reaction 2d, to which was added _{H 2 O (100mL), CH} 2 Cl 2 and extracted (50mL x 3), the organic phase was dried over anhydrous MgSO _4, solvent was removed by rotary evaporation was dissolved in a small amount (2mL) CH in ₂ Cl _2, in MeOH (100 mL) sedimentation, filtered off with suction, washed with anhydrous MeOH, residue redissolved in CH ₂ Cl _2, the settling and again filtered off with suction, and dried in vacuo after 80 deg.] C 8h to give a white solid 413 mg, yield The rate is 96%.

Nuclear magnetic characterization ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.33 (dd, J = 18.6, 9.4 Hz, 8H), 7.11 (d, J = 7.8 Hz, 1H), 7.04 (d, J = 8.2 Hz, 1H) ), 6.93 (s, 1H), 3.27 (d, J = 4.0 Hz, 1H); ¹³ C NMR (126 MHz, CDCl ₃ ) δ 151.73, 150.39, 145.90, 145.87, 138.47, 138.22, 131.41, 128.76, 127.94 (q, J = 286.9 Hz). 124.14, 122.52, 120.56, 64.98 (q, J = 23.6 Hz). 29.70, 29.52; ¹⁹ F NMR (376 MHz, CDCl ₃ ): δ - 58.35.

Compared with the conventional polycarbonate-based polymer, the polymer prepared above has better heat resistance and electrical properties.

Example 11 Preparation of Polyimide Containing Benzocyclobutene Structure

To a solution of trifluorovinylbenzocyclobutenediamine (737 mg) in NMP was added 4,4'-oxydiphthalic anhydride (620 mg) at room temperature. After stirring for 48 hours, acetic anhydride (2 ml) and pyridine (2 ml) were added. After stirring at room temperature for 12 hours, the solution was poured into methanol (500 ml) and then filtered. The obtained residue was redissolved with a small amount of chloroform, and was again allowed to precipitate, suction filtered, and dried in vacuo to give 1.28 g of pale pink solid.

Nuclear magnetic characterization ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.02 (d, J = 8.1 Hz, 2H), 7.61 to 7.30 (m, 12H), 7.07 to 6.97 (m, 2H), 6.90 (s, 1H) , 3.18(s,4H); ¹³ C NMR (126MHz, CDCl ₃ ): δ166.19,166.06,161.32,145.86,145.84,139.99,138.04,134.64,131.20,130.90,128.90,127.33,126.43,125.73,125.02,124.28, 122.50, 114.16, 29.73, 29.52; ¹⁹ F NMR (376 MHz, CDCl3): δ - 58.14.

Compared with the conventional polyimide-based polymer, the polymer prepared above has better heat resistance and electrical properties. The 5% weight loss temperature in the nitrogen atmosphere of the obtained polymer was 523 ° C as measured by thermogravimetric analysis (TGA), and the carbon residual ratio was 56.7% at 1000 ° C.

Example 12 Preparation of Polyimide Containing Benzocyclobutene Structure

To a solution of trifluorovinylbenzocyclobutenediamine (737 mg) in NMP, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (888 mg) was added at room temperature. . After stirring for 48 hours, acetic anhydride (2 ml) and pyridine (2 ml) were added. After stirring at room temperature for 12 hours, the solution was poured into methanol (500 ml) and then filtered. The obtained residue was redissolved with a small amount of chloroform, and was again allowed to precipitate, suction filtered, and dried in vacuo to give a pale pink solid, 1.48 g, yield 95%.

NMR Characterization _{^{1 H NMR (400MHz, CDCl 3}} ): δ8.13 ~ 7.80 (m, 6H), 7.52 ~ 7.27 (m, 8H), 7.07 ~ 6.85 (m, 3H), 3.17 (s, 4H); 13 C NMR (126 MHz, CDCl ₃ ): δ 166.02, 165.89, 145.91, 140.27, 139.34, 137.99, 136.16, 132.72, 132.41, 130.99, 128.89, 125.82, 125.49, 124.33, 123.43 (q, J=275.3 Hz), 122.55, 65.29, 29.74, 29.53; ¹⁹ F NMR (376 MHz, CDCl3): δ - 58.15, - 63.24.

Compared with the conventional polyimide-based polymer, the polymer prepared above has better heat resistance and electrical properties. The 5% weight loss temperature in the nitrogen atmosphere of the obtained polymer was 514 ° C as measured by thermogravimetric analysis (TGA), and the carbon residual ratio at 5 ° C was 56.1%.

Example 13 Modification of an epoxy resin by benzocyclobutene bisamine.

Trifluorovinylbenzocyclobutene bisamine (46.9 g) was uniformly blended with epoxy resin F151 (100 g) at 80 °C. Thereafter, the mixture was heated to 130 ° C for 1 hour, and further heated to 200 ° C for 2 hours to obtain a yellow solid.

Using the thermogravimetric analysis (TGA) test, the 5% weight loss temperature of the obtained solid was 384 ° C, which was significantly higher than the 5% weight loss temperature of pure epoxy resin at 373 ° C.

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims (12)

A class of compounds having the structure of formula I below:

In the formula, Each R is independently selected from the group consisting of -OH, -NH ₂ ; Each R _{1 is} independently selected from the group consisting of H, C1-C4 alkyl; R _{2 is} selected from the group consisting of H, a C1-C4 alkyl group, and a C1-C4 halogenated alkyl group. The compound of formula I according to claim 1, wherein each R is independently selected from the group consisting of -OH, -NH ₂ ; Each R _{1 is} independently selected from the group consisting of H, —CH ₃ ; R _{2 is} selected from the group consisting of H, -CH ₃ , and -CF ₃ . The method for preparing a compound I according to claim 1, wherein the method comprises the steps of:

(i) reacting a compound of formula II with a compound of formula IV, or a salt thereof with an acid, in an inert solvent to provide a compound of formula I; Wherein each group is as defined in claim 1; preferably, in the step (i), the molar ratio of the compound of the formula II to the compound of the formula IV is from 1:1.5 to 5, preferably 1:2.5. ~3. The method according to claim 3, wherein when each R is -OH, the method comprises the steps of: (ia) reacting a compound of formula II with a compound of formula IV in a polar solvent to provide a compound of formula I, and said step (ia) is carried out in the presence of an acid; preferably, said acid is a protic acid, more Preferably, it is selected from the group consisting of HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or a combination thereof. The method according to claim 3, wherein when each R is -NH ₂ , the method comprises the steps of: (ib) reacting a compound of formula II with a compound of formula IV or a salt thereof with an acid in a polar solvent to provide a compound of formula I; Preferably, the step (ib) is carried out in the presence of an acid; preferably, the acid is selected from the group consisting of HCl, HBr, H ₂ SO ₄ , CH ₃ SO ₃ H, CF ₃ SO ₃ H, or Its combination. The method for preparing a compound of formula II according to claim 1, wherein the method further comprises the steps of:

(ii) reacting a compound of formula III (4-halobenzocyclobutene) with an acylating reagent in a polar solvent to provide a compound of formula II; Wherein X is selected from the group consisting of halogen; the remaining groups are as defined in claim 1. The method according to claim 6, wherein said step (ii) further comprises: preparing an aryl anion with 4-halobenzocyclobutene in a polar solvent, and then reacting with an acylating reagent To obtain a compound of formula II; preferably, in the step (ii), the method for preparing an aryl anion using 4-halobenzocyclobutene is selected from the group consisting of: (1) subjecting a compound of the formula III to lithium halide exchange with an alkyllithium reagent to obtain an aryllithium salt; preferably, when the aryl anion is prepared by the method (1), the X is Br; (2) reacting a compound of the formula III with magnesium metal to obtain an aryl Grignard reagent; preferably, when the aryl anion is prepared by the method (2), the X is Cl or Br. A compound of the following formula II:

Wherein R _{2 is} selected from the group consisting of C1-C4 haloalkyl (preferably fluoroalkyl). Use of the compound I according to claim 1 for: (a) preparing a thermosetting material; (b) modifying existing products or preparing new materials as additives to bisphenol or bisamine products; (c) for the preparation of a polymer intermediate. An article characterized by comprising the compound I according to claim 1 as an additive; preferably, the article is an epoxy resin article. A polymer characterized in that the polymer is prepared by homopolymerization or copolymerization of the compound I according to claim 1 as a monomer. The polymer of claim 11 wherein said polymer has a structure selected from the group consisting of: