TWI422620B - Process for manufacturing flame-retardant and phosphorous-modified hardener - Google Patents

Description

Method for producing flame retardant and phosphorus modified hardener

This invention relates to a method of making a flame retardant and phosphorus modified hardener. More specifically, it relates to a method of preparing a phosphorus-modified flame retardant hardener having excellent flame retardancy and heat resistance.

Today's plastics are used in a wide range of industrial applications such as electronics, conveyors, building materials and more. However, plastics containing carbon, oxygen, hydrogen, etc. are easily burned, and in consideration of safety in the event of fire, there is a gradual need for improved flame retardancy.

In general, fire requires fuel, oxygen, and energy, and if it does not meet any of these requirements, it does not catch fire. That is, the method of plastic flame retardancy can be achieved by eliminating at least one of these necessary factors. The flame retardant hardener means a substance which is chemically or physically added with a high flame retardant compound such as a halogen, a phosphorus and/or a nitrogen compound, a metal oxide or the like, which delays ignition or combustion and prevents combustion from spreading.

Flame retardant hardeners are classified into various types in terms of their type and/or use, and are generally classified into a reactive hardener and an additive hardener. The reactive hardener contains a functional group capable of reacting in a molecule and is not affected by external conditions, so that the flame retarding effect is maintained. On the other hand, the additive type hardener is physically mixed, added or dispersed in a plastic substance to induce a flame retardant effect, and is generally used for a thermoplastic plastic material.

A wide variety of additive or reactive flame retardant hardeners are well known in the art, and added flame retardant hardeners may include, for example, tricresyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, trimethylphenyl. Phosphate ester, tris(bromochloropropyl)phosphate, tris(dichloropropyl)phosphate, and the like. The reactive flame retardant hardener may include, for example, bromophenol, bromophenyl allyl ether, vinyl chloroacetate, ethylene glycol oxime, tetrabromobisphenol, and the like.

The reactive flame retardant hardener chemically reacts with the substrate and then permanently combines with the polymer structure. Conversely, the flame retardant substance in the additive type flame retardant hardener does not chemically react with the polymer matrix, but simply dissolves or disperses in the matrix, and thus is usually lost from the matrix.

The technique for imparting flame retardancy to an epoxy resin includes co-reacting with a halogen-containing compound (i.e., tetrabromobisphenol A) when synthesizing an epoxy resin or adding a halogen-containing compound to an epoxy resin composition. When such a halogen-based flame retardant hardener is used to impart flame retardancy to the epoxy resin composition, a toxic carcinogen such as polyhalogenated aromatic dioxin or dibenzofuran is formed during combustion of the flame retardant hardener. In particular, polybrominated compound-based flame retardant hardeners can cause the production of harmful carcinogens such as decabromophenyl dioxide and octabromophenyl ether. Further, regarding the halogen-based compound, gases generated during combustion such as HBr and HCl are harmful to the human body and corrode metals, so care must be taken when using the compound, for example, at a place where precision electronic equipment is installed. Conversely, phosphorus-containing flame retardant hardener systems are preferred for use in comparison to halogens, particularly bromine-containing flame retardant hardener systems, depending on environmental considerations.

However, the conventional non-halogen flame retardant hardener has a problem in that a large amount of the phosphorus-containing raw material is introduced to impart satisfactory flame retardancy to the epoxy molecular structure, which causes gelation or a decrease in hardening density due to an increase in molecular weight. As a result, the hardened product has a drawback that the inherent physical properties such as heat resistance, adhesion, and thermal stability are drastically deteriorated. In other words, although the flame retardancy is sufficiently ensured by reacting a large amount of the phosphorus-containing raw material, a compound having a relatively large molecular structure is produced, resulting in a space barrier effect and a low hardening density. As a result, thermal properties and adhesive properties are degraded. However, due to environmental regulations such as RoHS, PoHS, etc., some materials (ie, lead, cadmium, hexavalent chromium) are used on conventional thermal insulation materials for printed circuit boards and other motor/electronic components and high reliability semiconductor packaging materials. Partially or completely restricted. Therefore, there is an increasing expectation today for suitable physical properties including flame retardant polymer materials such as high heat resistance, thermal stability, viscosity, low absorbency, and the like. In particular, due to the increased soldering temperature during the manufacture of printed circuit boards, there is still a novel technique for synthesizing non-flame retarding binary compounds having unique properties such as high heat resistance, thermal stability, low moisture absorption, high viscosity, and the like. There is still a need for efficient production of non-flame retardant binary compounds.

The present invention is directed to solving the above-mentioned problems, and a first object of the present invention is to provide a method for preparing a phosphorus-modified flame retardant hardener which can be reduced as an intermediate between a resole phenolic resin compound Dehydration.

Another object of the present invention is to provide a halogen-free, phosphorus-modified flame retardant hardener having excellent flame retardancy, adhesion, mechanical and chemical properties.

In order to accomplish the above first object, the present invention provides a method for preparing a phosphorus-modified flame retardant hardener comprising: 1) reacting a phenol compound with an aldehyde compound in the presence of a basic catalyst to prepare a resol resin compound And 2) directing and dehydrating the prepared resol resin compound and a phosphorus-containing compound in a solvent to form a phosphorus-modified flame retardant hardener.

According to an exemplary embodiment of the present invention, the above phenol compound may comprise at least one compound selected from the group consisting of the following formulas 1 to 4:

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y being F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and n each being 1 An integer of up to 10.

According to a preferred embodiment of the present invention, the phenol compound and the aldehyde compound of the above step 1) can be reacted together with a relative molar ratio of 1:1 to 1:5.

According to another preferred embodiment of the present invention, the phenolic compound may comprise a solvent selected from the group consisting of phenol, cresol, ethylphenol, butanol, octylphenol, phenol, cumylphenol, methoxyphenol, ethoxylated phenol, At least one of a group consisting of naphthol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, and bisphenol.

According to another preferred embodiment of the present invention, the basic catalyst may comprise at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, and amines. .

According to another preferred embodiment of the present invention, the resol resin compound may be a phenol-aldehyde polymer.

According to another preferred embodiment of the present invention, the resol resin compound may comprise at least one compound selected from the group consisting of the following formulas 5 to 8:

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and each Z is F, S And SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of m is an integer of 0 to 5, and n is each an integer of 1 to 10.

According to another preferred embodiment of the present invention, the solvent may comprise a solvent selected from the group consisting of benzene, toluene, xylene, dioxane, DMF, DMSO, methanol, ethanol, butanol, propanol, glycol, ether and phenol. At least one of the groups.

According to another preferred embodiment of the present invention, the phosphorus-containing compound may comprise at least one compound selected from the group consisting of the following formulas 9 and 10:

Wherein R ₁ and R _{2 are} each independently H, substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, substituted or unsubstituted C ₁ to C ₁₀ aryl compound, substituted or unsubstituted C ₁ to C ₁₀ heteroaryl compound, Substituted or unsubstituted C ₁ to C ₁₀ decyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol group.

According to another preferred embodiment of the present invention, the phosphorus-containing compound may be 3,4,5,6-dibenzo-1,2-oxophosphonium-2-oxide (hereinafter referred to as "DOPO"), Dimethyl phosphate (hereinafter referred to as "DMPP") or diphenylphosphine oxide (hereinafter referred to as "DPPO").

According to another exemplary embodiment of the present invention, the step 2) may include: reacting the resol resin compound with a solvent for 2 to 5 hours to obtain an alcoholy-soluble resol resin compound; and the alcoholysis The resol resin compound reacts with the phosphorus-containing compound to produce a phosphorus-modified flame retardant hardener.

According to another preferred embodiment of the present invention, the above alcoholy-soluble resol resin compound may be selected from the compounds represented by the following formulas 11 to 14:

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of which is H or Substituted or unsubstituted C ₁ to C ₁₀ alkyl, m is each an integer from 0 to 5, and n is each an integer from 1 to 10.

According to another preferred embodiment of the present invention, the resol resin compound may be reacted with a solvent in an amount of from 20 to 80 parts by weight based on 100 parts by weight of the solvent (hereinafter referred to as "part by weight").

According to another preferred embodiment of the present invention, the phosphorus-containing compound can be reacted with the alcohol-soluble resol resin compound in a relative molar ratio of from 0.5:1 to 1:1.

According to another preferred embodiment of the present invention, the phosphorus-modified flame retardant hardener may comprise at least one compound selected from the group consisting of the following formulas 15 to 18:

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of which is H or Substituted or unsubstituted C ₁ to C ₁₀ alkyl, Q is , R ₁ and R ₂ are each H, substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkyne a substituted, unsubstituted or substituted C ₁ to C ₁₀ aryl compound, substituted or unsubstituted C ₁ to C ₁₀ alkyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol group m is each an integer from 0 to 5, and n is each an integer from 1 to 10.

In order to accomplish the second object, the present invention provides a phosphorus-modified flame retardant hardener produced by the aforementioned method.

Hereinafter, the terms used herein are succinctly explained.

Unless otherwise indicated, the term "resin phenolic resin reaction" means the production of a compound via an addition reaction (first reaction) of a phenol and formaldehyde under basic conditions. The product of the resol phenol resin reaction is condensed (second reaction) during high temperature dehydration to produce a resol phenolic resin. In the present invention, an addition reaction of phenol with formaldehyde is employed, and the product of the addition reaction (first reaction product) used can react the phenol with an excess of formaldehyde.

The "resin phenol resin compound" is intended to include a compound produced by a reaction of a resol resin.

Unless otherwise indicated, the term "substituted or unsubstituted" with a substituent is intended to include both substituted and unsubstituted substituents. When substituted, the substituent is at least one group selected from the group consisting of, but not limited to, alkyl, mercapto, cycloalkyl (including bicycloalkyl and tricycloalkyl), Haloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, alcohol (-OH), ketone, arylalkoxy, aryloxy, thiol, alkylthio, aryl Alkylthio, carbonyl, ether, ester, thiol, phosphorus, sulfur, phosphate, phosphite, hypophosphite, sulfate, disulfide and protective derivatives thereof. The substituents are generally concerned with the various substituents well known in the art and are not subject to their particular limitations. Optionally, such substituents may also be substituted or unsubstituted.

As used herein, the term "aryl" refers to an aryl group having at least one ring containing a shared π-electron system, and includes carbocyclic aryl (eg, phenyl) and heterocyclic aryl (eg, pyridine, furan,吲哚, 嘌呤). This term is intended to include a single ring or a fused ring polycyclic (ie, a ring of carbon atoms sharing a contiguous portion).

The term "heteroatom" refers to an atom other than carbon and hydrogen.

The term "heteroalkyl" means that at least one carbon atom in the alkyl group is substituted with another heteroatom.

The term "heteroaryl" means an aryl group containing at least one heterocyclic ring, and more specifically, any substituted aryl group having 5 or 6 atoms in each ring. The heteroaryl group preferably contains one or two oxygen atoms, one or two sulfur atoms and/or one to four nitrogen atoms in one ring, and may be bonded to other portions of the ring via a carbon atom or a hetero atom. Examples of the heteroaryl group may include a furyl group, a thienyl group, a pyridyl group, an oxazolyl group, a pyrrolyl group, a fluorenyl group, a quinolinyl group, and an isoquinolinyl group. Examples of the substituent may include at least one selected from the group consisting of a hydrocarbon group, a substituted hydrocarbon group, a ketone, a hydroxyl group, a protected hydroxyl group, a decyl group, a decyloxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, and a sulfur. Alcohols, ketals, acetals, esters and ethers.

The term "heterocycle" means any of a monocyclic or bicyclic aryl group and a non-aryl group having at least one hetero atom (preferably, five or six atoms) in each ring and optionally substituted. , fully saturated or unsaturated. The heterocyclic group may preferably have one or two oxygen atoms, one or two sulfur atoms and/or one to four nitrogen atoms, and is preferably bonded to other portions of the molecule via a carbon atom or a hetero atom. Examples of the heterocyclic group may include a furyl group, a thienyl group, a pyridyl group, an oxazolyl group, a pyrrolyl group, a fluorenyl group, a quinolyl group, and an isoquinolyl group. Examples of the substituent may include at least one selected from the group consisting of a hydrocarbon group, a substituted hydrocarbon group, a ketone, a hydroxyl group, a protected hydroxyl group, a decyl group, a decyloxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, a thiol group. , ketals, acetals, esters and ethers.

The term "alkyl" means an aliphatic hydrocarbon group, and the alkyl moiety may be "saturated alkyl", meaning that it does not contain an alkene or alkyne moiety. The alkyl moiety can also be an "unsaturated alkyl" moiety, meaning that it contains at least one olefin or alkyne moiety. The term "olefin" means a group consisting of at least two carbon atoms and at least one carbon-carbon double bond, and the term "alkyne" means a chain of at least two carbon atoms and at least one carbon-carbon bond. The basis of the composition. Whether saturated or unsaturated, the alkyl moiety can be branched, straight or cyclic. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

The term "mercapto" refers to the residue remaining after removal of a hydroxyl group from the -COOH group of an organic carboxylic acid, and is represented, for example, by RC(O)-, wherein R is R ¹ , R ¹ O- or R ¹ S- And R ¹ is a hydrocarbon group, a hetero atom-substituted hydrocarbon group or a heterocyclic ring, and R ² is a hydrogen group, a hydrocarbon group or a substituted hydrocarbon group.

The term "aryl" means an optionally substituted homocyclic aryl group, preferably a monocyclic or bicyclic ring having 6 to 12 carbon atoms, such as phenyl, biphenyl, naphthyl, substituted benzene. Substituted, substituted biphenyl or substituted naphthyl. Phenyl and substituted phenyl are preferred examples.

The terms "hydrocarbon" and "hydrocarbyl" mean an organic compound or residue consisting solely of carbon and hydrogen. The above residues also include alkyl, alkenyl, alkynyl and/or aryl groups substituted with aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkaryl and alkynyl groups. Unless otherwise indicated, this residue preferably contains from 1 to 20 carbon atoms.

Other terms may be interpreted as meanings as understood in the general art related to the present invention.

The phosphorus-modified flame retardant hardener prepared according to the method of the present invention does not involve self-dehydration due to the acidic property of the phosphorus-containing compound added to the resol resin compound, which is an intermediate product And the side reaction can be reduced, and then the yield is remarkably improved.

In addition, the phosphorus-modified flame retardant hardener prepared according to the method of the present invention exhibits excellent flame retardancy, heat resistance and physical and chemical properties, and is sufficient to use the hardener as an additive in polycarbonate or other engineering plastics, for example ABS, HIPS, etc., and can also be used as a raw material for epoxy resins, cyanate resins, and acrylate resins, and/or as a hardener for epoxy resins.

Thus, the hardener of the present invention can be used for various applications including, for example, insulating materials for high reliability motor/electronic components such as EMC, various synthetic materials such as PCB substrates, and insulation requiring excellent flame retardancy and thermal stability. Plates, adhesives, coatings, coatings, etc.

The invention will be more clearly understood from the following detailed description.

As described above, the conventional non-halogen flame retardant hardener for overcoming the problem of the halogen-based flame retardant hardener has an advantage of reducing environmental pollution. However, compared with the halogen-based hardener, the non-halogen-based hardener has a problem of a degraded flame retardant effect and reduced physical and chemical properties.

Accordingly, the present invention provides a method for preparing a phosphorus-modified flame retardant hardener, which has an excellent flame retardant effect compared to a conventional non-halogen flame retardant hardener. And physical properties without halogen.

More specifically, the method for preparing a phosphorus-modified flame retardant hardener comprises: 1) reacting a phenol compound with an aldehyde compound in the presence of a basic catalyst to prepare a resol resin compound; and 2) in a solvent The prepared resol resin compound and the phosphorus-containing compound are guided to be dehydrated to form a phosphorus-modified flame retardant hardener.

First, in the step 1), the phenol compound is reacted with an aldehyde compound in the presence of a basic catalyst. More specifically, the phenol compound used herein may be selected from conventional phenol compounds which are generally used in the art, and is not particularly limited, and preferably contains any one selected from the phenol compounds represented by Formulas 1 to 4. More preferably, the phenol compound represented by Formula 1 may be a phenol or a cresol, and the phenol compound represented by Formula 2 may be bisphenol A, bisphenol F, bisphenol AD, bisphenol S or the like. Similarly, the phenol compound represented by Formula 3 may be a phenol novolac or a cresol novolac, and the phenol compound represented by Formula 4 may be a bisphenol A phenol resin or a bisphenol F phenol aldehyde. Resin, bisphenol S phenolic resin, bisphenol AD phenolic resin, and the like. The above phenolic compound has the advantages of improved flame retardant effect and physical properties.

With respect to Formulas 1 to 4, X is each H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, And n is each an integer of 1 to 10.

The basic catalyst is not particularly limited as long as it is used for a reactive phenol resin reaction, and may preferably comprise a commercially available basic catalyst selected from sodium hydroxide, potassium hydroxide, lithium hydroxide or hydrogen. Magnesium oxide, sodium carbonate, potassium carbonate, calcium carbonate and amines.

In order to guide the reaction of the resol phenol resin, the aldehyde compound is not particularly limited as long as it can react with the phenol compound, and may preferably contain any one selected from the group consisting of formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, and alkyl group substitution. Aldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, furfural, and the like.

Step 1) comprises reacting a phenol compound with an aldehyde compound under specific reaction conditions in the presence of a basic catalyst, wherein the phenol compound reacts with the aldehyde compound in a relative molar ratio of 1:1 to 1:5. This reaction can be carried out at 30 to 100 ° C for 1 to 5 hours.

The resol resin compound is produced by the reaction of the soluble phenol resin of the step 1), and the produced resol resin compound may comprise any one selected from the group consisting of the resol resin compounds represented by Formulas 5 to 8. More preferably, the resol phenol resin compound represented by Formula 5 may be a phenol resol resin compound, and the resol phenol resin compound represented by Formula 6 may be used for the viewpoint of achieving a flame retarding effect and excellent physical properties. In the case of a bisphenol A resol resin compound, the resol resin compound represented by Formula 7 may be a phenol resin resol resin compound, and the resol resin compound represented by Formula 8 may be bisphenol A. A phenolic resin resol resin compound.

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of which is H or Substituted or unsubstituted C ₁ to C ₁₀ alkyl, m is each an integer from 0 to 5, and n is each an integer from 1 to 10.

Meanwhile, the resol resin compound can be obtained by reacting a phenol with an excess of an aldehyde in the presence of a basic catalyst, and in this case, an unreacted aldehyde and a basic catalyst may remain. This residual unreacted aldehyde may react with the phosphorus-containing compound without a catalyst, resulting in deterioration of the flame retardant effect and physical properties. Furthermore, the residual basic catalyst can cause self-polymerization of the resol resin compound during step 2). Due to the chlorination of the catalyst with the acidic phosphorus-containing compound, the catalyst is not involved in the reaction of the resol phenolic resin, which subsequently causes polymerization of the final product (i.e., the phosphorus-modified compound) or reduces its phosphorus content. Accordingly, the present invention may further comprise a method of removing both residual basic catalyst and residual aldehyde comprising using an appropriate acidic catalyst such as sulfuric acid, nitric acid or phosphoric acid in an aqueous solution to neutralize the residue and washing the neutralized residue. The product. However, the removal method is not particularly limited to the above method, and may be selected from any conventional separation technique.

Next, in the step 2), the resol resin compound prepared in the step 1) is dehydrated together with the phosphorus-containing compound in the presence of a solvent to produce a phosphorus-modified flame retardant hardener. In particular, in order to impart flame retardancy, any reactive phosphorus-containing compound known and used in the art can be used. The phosphorus-containing compound may comprise any one selected from the group consisting of phosphorus-containing compounds represented by Formulas 9 and 10, preferably DOPO (represented by Formula 10), DPPO (represented by Formula 9), DMPP (represented by Formula 9) ), etc., but there are no special restrictions.

Wherein R ₁ and R _{2 are} each independently H, substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, substituted or unsubstituted C ₁ to C ₁₀ aryl compound, substituted or unsubstituted C ₁ to C ₁₀ heteroaryl compound, Substituted or unsubstituted C ₁ to C ₁₀ decyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol group.

The resol resin compound is a very unstable substance which self-polymerizes at a low temperature, and this self-polymerization occurs rapidly in a side reaction in the presence of a basic catalyst or an acidic catalyst. Therefore, in the case where the resol resin compound is directly reacted with the phosphorus-containing compound in a solvent, the resol resin compound does not react with the phosphorus-containing compound due to the acidic property of the phosphorus-containing compound, but instead causes the resol resin. Self-dehydration reaction between compounds. As a result, problems such as relatively low flame retardancy, physical properties, yield of the target flame retardant hardener, and the like are left due to the residual unreacted phosphorus-containing compound. Therefore, the step 2) of the present invention comprises first reacting a resol resin compound with a solvent to prepare an alcoholy-soluble resol resin compound, and then reacting the alcoholy-soluble resol resin compound with the phosphorus-containing compound, To produce the final product, that is, a phosphorus-modified flame retardant hardener. As a result of the above steps, the above side reaction is reduced, and a target flame retardant hardener having excellent flame retardancy and physical properties can be obtained in high yield.

In this regard, the resol resin compound is preferably reacted with a solvent for 2 to 5 hours. If the reaction time is less than 2 hours, the alcoholysis is not sufficiently performed, and the resol resin compound is dehydrated and self-polymerized, thereby causing polymerization of the phosphorus-modified flame retardant hardener and its flame retardancy. And degradation of physical properties. On the other hand, if the reaction time is more than 5 hours, the alcoholysis is carried out sufficiently to increase the yield of the target flame retardant hardener, but the treatment time of the reaction is prolonged, and then the productivity is considerably lowered. Further, it is preferred that the resol resin compound is reacted with a solvent in an amount of from 20 to 80 parts by weight based on 100 parts by weight of the solvent. If less than 20 parts by weight of the resol resin compound is added, the yield of the phosphorus-modified flame retardant hardener per batch is reduced, thereby considerably reducing the productivity. On the other hand, if more than 80 parts by weight of the resol resin compound is added, the amount of the solvent for the alcoholysis is reduced, thereby causing dehydration and self-polymerization of the partially resol resin compound. As a result, it is necessary to withstand the problem of polymerization of, for example, a phosphorus-modified flame retardant hardener and/or degradation of its flame retardancy and physical properties.

The solvent for use herein may comprise at least one selected from the group consisting of methanol, ethanol, butanol, propanol, glycols, ethers, and phenols. Benzene, toluene, xylene, dioxane, DMF, DMSO, etc. may also be added to these alcohol compounds. However, in the case where a ketone is used as a solvent, this solvent may cause side reaction with the phosphorus-containing compound, and thus is not preferable (see Table 1 below).

The reaction between the above-mentioned resol resin compound and a solvent can preferably produce the alcoholy-soluble resol resin compound represented by any one of Formulas 11 to 14.

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of which is H or Substituted or unsubstituted C ₁ to C ₁₀ alkyl, m is each an integer from 0 to 5, and n is each an integer from 1 to 10.

The alcoholy-soluble resol resin compound prepared according to the above method is reacted with any one of the phosphorus-containing compounds selected from the formulas 9 and 10 to produce the phosphorus-modified flame retardant hardener of the present invention.

In this regard, the phosphorus-containing compound and the alcohol-soluble resol resin compound are added in a relative molar ratio of from 0.5:1.0 to 1.0:1.0. If the molar ratio of the phosphorus-containing compound is less than 0.5, the non-reactive phenolic resin compound or the alcohol-soluble resol resin compound (ie, the unreacted resol resin compound) will be dehydrated or delisted. , causing the polymerization of the phosphorus-modified flame retardant hardener and the degradation of its flame retardancy and physical properties. On the other hand, if the molar ratio of the phosphorus-containing compound exceeds 1.0, the amount of the phosphorus-containing compound excessively increases, and the remaining unreacted materials, such as thermal properties, thermal stability, moisture retention stability, and the like, greatly Deterioration, although the phosphorus-modified flame retardant hardener has a high phosphorus content.

The phosphorus-modified flame retardant hardener of the present invention may comprise any one of Formulas 15 to 18, and preferably, for the improvement of flame retardancy and physical properties, such as the flame retardant represented by Formula 15 Phosphorus-modified phenolic hardener of a hardener, phosphorus-modified bisphenol A hardener of a flame retardant hardener represented by Formula 16, and phosphorus-modified by a flame retardant hardener represented by Formula 17 The phosphorus-modified bisphenol A phenolic resin hardener of the phenolic resin hardener and/or the flame retardant hardener represented by Formula 18 can be advantageously obtained as a final product (see Table 1 for details).

Wherein each X is H or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each Y is F, S, SO ₂ or a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, each of which is H or Substituted or unsubstituted C ₁ to C ₁₀ alkyl, Q is , R ₁ and R ₂ are each H, substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkyne a substituted, unsubstituted or substituted C ₁ to C ₁₀ aryl compound, substituted or unsubstituted C ₁ to C ₁₀ alkyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol group m is each an integer from 0 to 5, and n is each an integer from 1 to 10.

With respect to Formulas 1 to 18, the substituted group may preferably include a group substituted with at least one selected from the group consisting of an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol group, and a cyano group. .

The phosphorus content of the phosphorus-modified flame retardant hardener ranges from 1 to 15%, and preferably from 5 to 11%. If the phosphorus content is less than 1%, the minimum flame retardant effect is achieved. Since the phosphorus content exceeds 15%, the chemical structure modification is virtually impossible.

Considering the balance between the modified mechanical properties and the improved flame retardant properties, the flame retardant hardener of the present invention prepared according to the above method may be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the resin, and is preferably. It is 1 to 30 parts by weight. In this regard, the flame retardant hardener of the present invention can exhibit excellent flame retardancy, heat resistance, and physical and chemical properties, and is satisfactory for use as a polycarbonate or an additive for other engineering plastics such as ABS, HIPS, and the like. A curing agent which is a raw material of an epoxy resin, a cyanate resin, and an acrylate resin, and/or an epoxy resin can also be used. Therefore, the flame retardant hardener of the present invention can be used in various applications, including insulating materials such as EMC's highly reliable motor/electronic components, various composite materials such as PCB substrates, and insulating sheets requiring excellent flame retardancy and thermal stability. , adhesives, coatings, coatings, etc.

Preferred embodiments of the invention will be described in detail in accordance with the following examples. However, the examples are not intended to limit the scope of the invention, and are intended to provide a more specific understanding of the invention.

Example 1

An aqueous solution containing 228 g (1 mol) of bisphenol A, 216 g (3 mol) of trioxane, 30 g of water and 10 g of 50% sodium hydroxide is placed in a reaction bath, followed by heating at 50 ° C under heating and stirring 5 hour. Thereafter, after adding 100 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 100 g of water to separate and obtain a bisphenol A resol resin compound (304.3 g, yield 94.8%). By adding this resol resin compound to 610 g of methanol, the alcoholysis of the resol resin compound was carried out at 70 ° C (T) for 5 hours with stirring. Thereafter, 522.15 g (2.417 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol portion. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 749 g of a phosphorus-modified bisphenol A flame retardant hardening compound having a phosphorus content of 9.3% (yield 91.9%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 2

An aqueous solution containing 228 g (1 mol) of bisphenol A, 108.4 g (1.5 mol) of trioxal, 30 g of water and 5 g of 50% sodium hydroxide was placed in a reaction bath, followed by heating and stirring at 50 ° C Reaction for 5 hours. Thereafter, after adding 76 g of water, neutralization was carried out using 2.5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 76 g of water to separate and obtain a bisphenol A resol resin compound (260.6 g, yield 95%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 521 g of methanol at 70 ° C (T) with stirring. Thereafter, 261.6 g (1.211 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 460 g of a phosphorus-modified bisphenol A flame retardant hardening compound having a phosphorus content of 7.38% (yield 91.26%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 3

An aqueous solution containing 228 g of bisphenol A, 288.4 g (4 mol) of trioxal, 30 g of water and 14 g of 50% sodium hydroxide was placed in a reaction bath, followed by a reaction at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 116 g of water, neutralization was carried out using 6.7 g of 0.1 N sulfuric acid. Then, the product was washed three times with 116 g of water to separate and obtain a bisphenol A resol resin compound (323 g, yield 92%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 646 g of methanol under stirring at 70 ° C (T). Thereafter, 675.6 g (3.128 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol portion. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 883 g of a phosphorus-modified bisphenol A flame retardant hardening compound having a phosphorus content of 10.43% (yield 87.42%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 4

An aqueous solution containing 94.11 g (1 mol) of phenol, 90.32 g (1.25 mol) of trioxal, 30 g of water and 3.3 g of 50% sodium hydroxide was placed in a reaction bath, followed by heating and stirring at 50 ° C Reaction for 5 hours. Thereafter, after adding 41.5 g of water, neutralization was carried out using 1.67 g of 0.1 N sulfuric acid. Then, the product was washed three times with 41.6 g of water to separate and obtain a phenol resol resin compound (127.5 g, yield 96%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 255 g of methanol under stirring at 70 ° C (T). Thereafter, 207.36 g (0.96 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 291 g of a phosphorus-modified phenol flame retardant hardening compound having a phosphorus content of 9.59% (yield 90%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 5

An aqueous solution containing 108.14 g of cresol, 90.32 g (1.25 mol) of trioxal, 30 g of water and 3.3 g of 50% sodium hydroxide was placed in a reaction bath, followed by a reaction at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 45 g of water, neutralization was carried out using 1.67 g of 0.1 N sulfuric acid. Then, the product was washed three times with 45 g of water to separate and obtain a cresol novolak resin compound (139.5 g, yield 95%). The alcoholysis of the resol resin compound was carried out by stirring at 70 ° C (T) for 5 hours by adding this resol resin compound to 279 g of methanol. Thereafter, 207.36 g (0.96 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 299 g of a phosphorus-modified cresol flame retardant hardening compound having a phosphorus content of 9.19% (yield 90%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 6

An aqueous solution containing 356 g (1 mole) of phenolic resin, 216 g (3 moles) of paraformaldehyde, 30 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by reaction at 50 ° C for 5 hours under heating and stirring. . Thereafter, after adding 130 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 130 g of water to separate and obtain a phenol-soluble phenol resin compound (408 g, yield: 90.8%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 816 g of methanol under stirring at 70 ° C (T). Thereafter, 500.12 g (2.315 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 814 g of a phosphorus-modified phenolic resin flame retardant hardening compound having a phosphorus content of 8.38% (yield 90.7%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 7

An aqueous solution containing 760 g (1 mol) of bisphenol A phenolic resin, 216 g (3 mol) of trioxane, 30 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by heating and stirring at 50 ° C. The reaction was carried out for 5 hours. Thereafter, after adding 213 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 213 g of water to separate and obtain a bisphenol A resol resin compound (776 g, yield: 91.0%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 1552 g of methanol at 70 ° C (T) with stirring. Thereafter, 501.2 g (2.320 mol) of DOPO was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 1161.31 g of a phosphorus-modified phenolic resin flame retardant hardening compound having a phosphorus content of 5.88% (yield 86.24%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 8

An aqueous solution containing 228 g (1 mol) of bisphenol A, 216 g (3 mol) of trioxane, 30 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by reaction at 50 ° C under heating and stirring. 5 hours. Thereafter, after adding 100 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 100 g of water to separate and obtain a bisphenol A resol resin compound (304.3 g, yield 94.8%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 610 g of methanol at 70 ° C (T) with stirring. Thereafter, 488.23 g (2.417 mol) of diphenylphosphine oxide was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol portion. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 728.9 g of a phosphorus-modified bisphenol A flame retardant hardening compound having a phosphorus content of 9.9% (yield 92%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Example 9

An aqueous solution containing 228 g (1 mol) of bisphenol A, 216 g (3 mol) of trioxane, 30 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by heating at 50 ° C under stirring and stirring 5 hour. Thereafter, after adding 100 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 100 g of water to separate and obtain a bisphenol A resol resin compound (304.3 g, yield 94.8%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 610 g of methanol at 70 ° C (T) with stirring. Thereafter, 265.87 g (2.417 mol) of dimethyl phosphite was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol fraction. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thereby obtaining 500 g of a phosphorus-modified bisphenol A flame retardant hardening compound having a phosphorus content of 14.22% (yield 89.3%).

FT-IR results: phenol-hydroxy group: 3300 cm ^-1 , P = O: 1200 cm ^-1 / 1280 cm ^-1 , PCO (aryl): 972 cm ^-1 , PC (aryl) 1424 cm ^-1 .

Comparative Example 1

800 g of novolac epoxy resin, YDPN-638 (manufactured by Kukdo Chemical Co., Ltd., EEW: 180 g/eq.), 200 g of DOPO, and ethyl iodide ethyl iodide (ETPPI) as a catalyst were slurried at 160 ° C. The polymerization was carried out for 6 hours, and thus a phosphorus-modified epoxy resin (EEW: 290 g/eq., phosphorus content: 2.7%) was prepared.

Comparative Example 2

The procedure of Example 1 was repeated except that water was used instead of methanol as a solvent to produce a flame retardant compound.

Comparative Example 3

The procedure of Example 1 was repeated to produce a flame retardant compound, except that the resol resin compound was simultaneously reacted with methanol and DOPO to replace the sequential reaction with these materials.

Comparative Example 4

The procedure of Example 1 was repeated except that ethylmethylketone was used in place of methanol to produce a flame retardant compound.

Experimental example

In order to evaluate the physical properties of the phosphorus-modified flame retardant hardener compound prepared in the above examples and comparative examples, according to the composition compositions shown in Table 1 below, these compounds were each mixed with the components listed in Table 1 below. .

More specifically, according to each of these compounds, the other components of the composition shown in Table 1 were mixed to prepare a varnish. The varnish is injected into the glass fibers to form a prepreg. Then, the prepreg was heated at 175 ° C for 5 minutes to convert the prepreg into a semi-hardened state, after which an eight-fold sample was formed. The sample was pressed at 190 ° C and 25 kgf / cm ^{2 for} 15 minutes and then pressed at 40 kgf / cm ^{2 for} 120 minutes. The compressed sample was cooled using a cooler for 30 minutes.

The flame retardancy of the sample was tested according to the UL-94 standard method.

The glass transition temperature of the sample was tested using a differential scanning calorimeter (DSC, 20/min).

The peel strength of the sample was determined according to the GIS C-6471 standard method.

According to Table 1 above, Dicy represents dicyanamide as a latent curing agent, 2MI represents 2-methylimidazole as a hardening accelerator, MCs represents 2-methoxyethanol as a solvent, and YDB-128 represents 186 g/eq equivalent. Bisphenol epoxy resin (Kukdo Chemical Co., Ltd.), and YD-011 indicates 475 g/eq equivalent of bisphenol epoxy resin (Kukdo Chemical Co., Ltd.).

As shown in Table 1, it was found that the flame retardant compounds obtained in Examples 1 to 9 had excellent glass transition temperatures and peel strengths as compared with those obtained in Comparative Examples 1 to 4.

As apparent from the above description, the phosphorus-modified flame retardant hardener prepared according to the above method of the present invention can be used in various applications including, for example, various composite materials such as a PCB substrate, and an insulating sheet, an adhesive, and a coating agent. , paint, etc.

Claims (6)

A method for preparing a phosphorus-modified flame retardant hardener, comprising: 1) 1:1 to 1:5 of a phenol compound and a monoaldehyde compound selected from at least one of the compounds represented by Formulas 1 to 4 The relative molar ratio is reacted in the presence of a basic catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate and amines. At least one of the present invention to prepare a resol resin compound selected from at least one of the compounds represented by Formulas 5 to 8; and 2) the prepared resol resin compound and a phosphorus-containing compound The solvent is guided to dehydrate to form the phosphorus-modified flame retardant hardener, wherein the step 2) comprises the steps of: a) using 20 to 80 parts by weight of the resol resin compound with respect to 100 parts by weight of the solvent. The amount is reacted with a solvent selected from at least one of the group consisting of methanol, ethanol, butanol, propanol, glycol, ether, and phenol for 2 to 5 hours to obtain any one selected from the group consisting of Formulas 11 to 14. Alcoholically soluble resol resin compound; and b) the phosphorus The compound and the alcoholy-soluble resol resin compound are subjected to alcoholysis at a relative molar ratio of from 0.5:1 to 1:1 to produce a phosphorus-modified flame retardant hardening selected from the compounds represented by Formulas 15 to 18. The phosphorus-modified flame retardant hardener is produced in a yield of 86% or more; Wherein each X is H or a substituted or unsubstituted C ₁ to C ₅ alkyl group, each Y being a substituted or unsubstituted C ₁ to C ₅ alkyl group, each Z being substituted or unsubstituted C ₁ to C ₅ alkyl, each of m is an integer from 1 to 5, and n is each an integer from 1 to 10; In Formulae 15 to 18, X is each H or a substituted or unsubstituted C ₁ to C ₅ alkyl group, each Y being a substituted or unsubstituted C ₁ to C ₅ alkyl group, each of which is substituted or Non-substituted C ₁ to C ₅ alkyl, Q is , R ₁ and R ₂ each substituted or unsubstituted C ₁ to C ₅ alkyl, substituted or unsubstituted C ₂ to C ₁₀ alkenyl, substituted or unsubstituted C ₂ to C ₁₀ alkynyl or The substituted or unsubstituted C ₅ to C ₁₀ aryl compound, each of m is an integer of 1 to 5, and each n is an integer of 1 to 10. The method of claim 1, wherein the phenol compound is selected from the group consisting of phenol , cresol, phenol, butyl phenol, octyl phenol, phenol, cumene phenol, methoxy phenol, ethoxy phenol, naphthol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD and At least one of the groups consisting of bisphenol. The method of claim 1, wherein the resol resin compound is a phenol-aldehyde polymer. The method of claim 1, wherein the solvent further comprises at least one selected from the group consisting of benzene, toluene, xylene, dioxane, DMF, and DMSO. The method of claim 1, wherein the phosphorus-containing compound is selected from at least one of the compounds represented by the following formulas 9 and 10: Wherein R ₁ and R _{2 are} each independently H, substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, substituted or unsubstituted C ₂ to C ₁₀ alkenyl, substituted or unsubstituted C ₂ to C ₁₀ alkynyl or substituted or unsubstituted C ₅ to C ₁₀ aryl compounds. The method of claim 1, wherein the phosphorus-containing compound is selected from the group consisting of 3,4,5,6-dibenzo-1,2-oxophosphonium-2-oxide, dimethyl phosphite, and diphenyl. At least one of the group consisting of phosphine oxides.