KR102342169B1 - Non Halogen Flame Retardant Copolymer, The Method of Manufacturing the Same and Composition Comprising the Same - Google Patents

Abstract

The present invention relates to a non-halogen flame retardant polymer, a method for preparing the same, and a flame retardant polymer composition comprising the same, and more particularly, a copolymer exhibiting excellent flame retardant properties, low dielectric properties, and a high glass transition temperature (Tg) of 170 ° C. or higher; It relates to a method for preparing the same and a flame retardant polymer composition comprising the same.
The non-halogen flame-retardant polymer according to the present invention includes an alkylphenol-based compound having low dielectric constant and dielectric loss factor and a bisphenol-based compound having excellent heat resistance as units, thereby exhibiting excellent flame retardant properties, low dielectric properties and high glass transition temperature. Therefore, the halogen-free flame-retardant polymer according to the present invention can be used as an electrical insulating material for high-speed signal transmission in a high-frequency region.

Description

Non-Halogen Flame Retardant Copolymer, The Method of Manufacturing the Same and Composition Comprising the Same

The present invention relates to a non-halogen flame retardant polymer, a method for preparing the same, and a flame retardant polymer composition comprising the same, and more particularly, a copolymer exhibiting excellent flame retardant properties, low dielectric properties, and a high glass transition temperature (Tg) of 170° C. or higher; It relates to a method for preparing the same and a flame retardant polymer composition comprising the same.

Recently, due to miniaturization and high-functionality of electronic devices, the wiring width of circuits has narrowed and the number of components mounted has increased. In order to ensure safety against fire when using such electronic devices, materials having heat resistance and flame retardancy are widely used as materials for substrates and parts.

In addition, the frequency band of signals used in communication electronic devices is shifting from the MHz region to the GHz band. Electrical signals have a characteristic that the transmission loss increases as the frequency increases. In order to improve the signal transmission speed in the high frequency region and reduce noise, the dielectric constant of the material used for the substrate and parts of the device needs to be low.

As a material satisfying these requirements, an epoxy resin is widely used. Epoxy resin is a material widely used in the fields of electrical and electronic materials, adhesives, paints, etc. because it exhibits high heat resistance, dimensional stability, high adhesive properties, excellent chemical resistance and electrical properties.

Techniques for imparting flame retardancy to such an epoxy resin include a technique of reacting a halogen-containing compound such as tetrabromobisphenol A together when synthesizing an epoxy resin, or a technique of adding a halogen-containing compound in the state of the epoxy resin composition. However, halogen-based flame-retardant curing agents have a problem in that toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated during combustion, so their use is currently limited.

Therefore, it is necessary to develop a new non-halogen flame retardant compound that does not contain halogen and exhibits flame retardancy, has excellent heat resistance, and has low dielectric properties to be suitable for high-frequency signal transmission.

Korean Patent Laid-Open Patent No. 2016-0051085, Non-halogen-based flame retardant polymer and manufacturing method thereof

The present inventors prepared a copolymer by copolymerizing an alkylphenol-based compound exhibiting low dielectric properties and a bisphenol-based compound having excellent heat resistance. (Tg) was confirmed, and the present invention was completed.

Accordingly, it is an object of the present invention to provide a copolymer that does not contain halogen and exhibits excellent flame retardancy, high glass transition temperature and low dielectric properties.

Another object of the present invention is to provide a method for preparing the non-halogen flame retardant polymer.

Another object of the present invention is to provide a flame retardant polymer composition comprising the non-halogen flame retardant polymer.

In order to achieve the above object, the present invention includes at least two repeating units selected from the following Chemical Formulas 1 to 4, at least one of the repeating units of Chemical Formulas 1 and 2, and among the repeating units of Chemical Formulas 3 and 4 Provided is a non-halogen flame retardant polymer comprising at least one, and a flame retardant polymer composition comprising the same:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,

X ₁ , X ₂ , a, b, c, and d are as described in the specification)

Also, the present invention

S1) reacting a monomer represented by the following formula (7), a monomer represented by the following formula (8), and formaldehyde in the presence of a catalyst to produce a primary polymer including a hydroxymethyl group;

S2) reacting the primary polymer with a C1 to C12 alcohol to produce a secondary polymer including an alkoxymethyl group; and

S3) generating a non-halogen flame retardant polymer by reacting the secondary polymer with a compound represented by Chemical Formula 9;

It provides a method for preparing a non-halogen flame retardant polymer comprising:

[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 7 and 8,

R ₁ , R ₃ , and Z ₁ are as described in the specification)

The non-halogen flame-retardant polymer according to the present invention includes an alkylphenol-based compound having low dielectric constant and dielectric loss factor and a bisphenol-based compound having excellent heat resistance as units to exhibit excellent flame retardant properties, low dielectric properties and high glass transition temperature. Therefore, the non-halogen flame retardant polymer according to the present invention can be used as an electrical insulating material for high-speed signal transmission in a high-frequency region requiring high heat resistance with a glass transition temperature of 170 ° C. or higher, as well as for smart phones and automotive applications.

Hereinafter, the present invention will be described in more detail.

non-halogen flame retardant polymer

The present invention provides a ratio comprising two or more repeating units selected from the following Chemical Formulas 1 to 4, at least one of the repeating units of Chemical Formulas 1 and 2, and at least one or more of the repeating units of Chemical Formulas 3 and 4 A halogen flame retardant polymer is provided.

The repeating units may be variously arranged in the form of random, alternating, or block.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,

이고, X₂는

이며, 이때 R₁은 H 또는 C1 내지 C5의 알킬기이고, R₂는 C1 내지 C12의 알콕시기이며, R₂의 알콕시기는 중합체 내에서 적어도 하나 이상이

로 치환되며, R₃는 H, C1 내지 C6의 알킬기, 또는 C6 내지 C12의 아릴기이고, Z₁은 SO, SO₂, C1 내지 C12의 알킬렌기이고,X ₁ is

and X ₂ is

In this case, R ₁ is H or a C1 to C5 alkyl group, R ₂ is a C1 to C12 alkoxy group, and R ₂ is at least one alkoxy group in the polymer.

substituted with, R ₃ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, Z ₁ is SO, SO ₂ , a C1 to C12 alkylene group,

a, b, c, and d are each an integer of 1 or more and 10 or less)

The C1 to C6 alkyl group mentioned herein is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, t- It may be a pentyl group or a hexyl group.

The C1 to C12 alkoxy group mentioned herein is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentoxy group, a hexyloxy group, 2- It may be a hydroxyethoxy group, a 2-methoxyethoxy group, a 3-methoxypropoxy group, or a phenoxy group.

The C6 to C12 aryl group mentioned herein may be a phenyl group unsubstituted or substituted with a C1 to C6 alkyl group.

The C1 to C12 alkylene group referred to in the present specification has -(CH ₂ ) _n - (n is an integer of 1 to 12) as a basic skeleton, and at least one hydrogen is a C1 to C11 alkyl group or C6 to C11 aryl It may be a structure unsubstituted or substituted with a group. In this case, a C6 to C10 aryl group may be included between _{the -(CH 2} ) _{n - CC bonds of the basic skeleton.}

가 혼재할 수 있는데, 중합체는 적어도 하나 이상의

치환기를 가짐으로써 난연 특성을 나타낼 수 있다. 구체적으로, 본 발명의 비할로겐 난연성 중합체에서 알콕시기와

의 비율은 9:1 내지 0:10 이다. In the non-halogen flame retardant polymer according to the present invention, R ₂ may be different for each repeating unit or even within the repeating unit. That is, the alkoxy group in the polymer

may be mixed, wherein the polymer comprises at least one

By having a substituent, it can exhibit flame retardant properties. Specifically, in the non-halogen flame retardant polymer of the present invention, the alkoxy group

The ratio is 9:1 to 0:10.

The non-halogen flame retardant polymer according to the present invention is a copolymer prepared by using an alkylphenol-based compound represented by the following formula (7) and a bisphenol-based compound represented by the following formula (8) as a comonomer.

[Formula 7]

[Formula 8]

(In Formulas 7 and 8,

R ₁ is H, or a C1 to C5 alkyl group,

R ₃ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group,

Z ₁ is SO, SO ₂ , or a C1 to C12 alkylene group)

In Chemical Formula 7, R ₁ is preferably an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, a neopentyl group, and a t-pentyl group, which are branched alkyl groups.

In Formula 8, R ₃ is preferably H, and Z is preferably -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(C ₆ H ₅ ) ₂ -, or -C(C ₆ H ₅ )(CH ₃ )-, more preferably -C(CH ₂ ) ₂ -.

The alkylphenol-based compound of Chemical Formula 7 exhibits low dielectric properties due to an increase in free volume of the cured product after curing due to the alkyl group, and the bisphenol-based compound of Chemical Formula 8 exhibits high heat resistance due to its low fluidity molecular structure. In the present invention, by copolymerizing such alkylphenol and bisphenol, a halogen-free flame retardant polymer having a low dielectric constant and a dielectric loss factor and a high glass transition temperature of 170° C. or higher was realized.

As described above, the non-halogen flame-retardant polymer according to the present invention necessarily includes one of the alkylphenol-based compounds represented by Formula 7 as the first monomer and one of the bisphenol-based compounds represented by Formula 8 as the second monomer, In addition to this, the third monomer may further include one of an alkylphenol-based or bisphenol-based compound different from the first and second monomers. In this case, the polymer further includes at least one or more repeating units selected from the following Chemical Formulas 5 and 6.

[Formula 5]

[Formula 6]

(In Formulas 5 and 6,

또는

이며, 이때 R₄는 H 또는 C1 내지 C5의 알킬기이고, R₂는 C1 내지 C12의 알콕시기이며, R₂의 알콕시기는 중합체 내에서 적어도 하나 이상이

로 치환되며, R₅는 H, C1 내지 C6의 알킬기, 또는 C6 내지 C12의 아릴기이고, Z₂는 SO, SO₂, C1 내지 C12의 알킬렌기이고,X ₃ is

or

In this case, R ₄ is H or a C1 to C5 alkyl group, R ₂ is a C1 to C12 alkoxy group, and the alkoxy group of R ₂ is at least one or more in the polymer.

substituted with, R ₅ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, Z ₂ is SO, SO ₂ , a C1 to C12 alkylene group,

e and f are each an integer of 1 or more and 10 or less,

일 때, R₄ 및 R₁는 서로 상이하고, X ₃ is

When , R ₄ and R ₁ are different from each other,

일 때, R₅ 및 R₃는 서로 상이하거나, Z₂ 및 Z₁는 서로 상이하다)X ₃ is

When , R ₅ and R ₃ are different from each other, or Z ₂ and Z ₁ are different from each other)

In this case, the repeating unit of Chemical Formulas 5 and 6 is preferably 0 to 20% by weight based on the total weight of the polymer)

The non-halogen flame retardant polymer according to the present invention preferably has a weight average molecular weight of 500 to 2500 g/mol. If the weight average molecular weight is less than 500 g/mol, there is a problem in that heat resistance is lowered, and if it exceeds 2500 g/mol, there is a problem of poor impregnation property, so it is appropriately adjusted within the above range.

The non-halogen flame-retardant polymer according to the present invention preferably contains phosphorus in an amount of 5 to 12% by weight to ensure flame retardant properties. If the phosphorus content is less than 5% by weight, the flame retardant effect is insignificant, so there is a disadvantage that a large amount of flame retardant auxiliary agent is required when mixing the resin.

non-halogen Method for producing flame retardant polymer

the present invention

S1) reacting a monomer represented by the following formula (7), a monomer represented by the following formula (8), and formaldehyde in the presence of a catalyst to produce a primary polymer including a hydroxymethyl group;

S2) reacting the primary polymer with a C1 to C12 alcohol to produce a secondary polymer including a benzene ring including an alkoxymethyl group; and

S3) generating a non-halogen flame retardant polymer by reacting the secondary polymer with a compound represented by Chemical Formula 9;

It provides a method for preparing a non-halogen flame retardant polymer comprising:

[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 7 and 8,

R ₁ is H or a C1 to C5 alkyl group, R ₃ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, and Z ₁ is SO, SO ₂ , a C1 to C12 alkylene group)

A method for producing a flame retardant polymer according to an embodiment of the present invention may be represented by the following Reaction Scheme 1.

[Scheme 1]

로 치환된다)(In Scheme 1, R ₂ is a C1 to C12 alkoxy group, and the alkoxy group of R ₂ is at least one or more in the polymer.

is replaced with)

Hereinafter, each step will be described in detail.

(1) Step S1

In step S1, copolymerization of the monomer represented by Formula 7 and the monomer represented by Formula 8 occurs in the presence of a catalyst, and at the same time, a hydroxymethyl group (-CH ₂ OH) is introduced into the benzene ring of the monomer and the reaction intermediate by formaldehyde. . The primary polymer produced at this time may be a random, alternating, or block copolymer.

The monomer represented by Formula 7 is an alkylphenol-based monomer, for example, p-isopropylphenol, p-isobutylphenol, pt-butylphenol, p-isopentylphenol, p-neopentylphenol, and pt-pentylphenol. phenol, preferably pt-butyl phenol (PTBP).

The monomer represented by Formula 8 is a bisphenol-based monomer, for example, bisphenol A (2,2-Bis (4-hydroxyphenyl) propane), bisphenol AP (1,1-Bis (4-hydroxyphenyl) -1-phenyl- ethane), bisphenol B(2,2-Bis(4-hydroxyphenyl)butane), bisphenol BP(Bis-(4-hydroxyphenyl)diphenylmethane), bisphenol C(2,2-Bis(3-methyl-4-hydroxyphenyl)propane ), Bisphenol E(1,1-Bis(4-hydroxyphenyl)ethane), Bisphenol F(Bis(4-hydroxyphenyl)methane), Bisphenol G(2,2-Bis(4-hydroxy-3-isopropyl-phenyl)propane ), bisphenol M(1,3-Bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bisphenol S(Bis(4-hydroxyphenyl)sulfone), bisphenol P(1,4-Bis(2-( 4-hydroxyphenyl)-2-propyl)benzene), bisphenol PH(5,5'-(1-Methylethyliden)-bis[1,1'-(bisphenyl)-2-ol]propane), bisphenol TMC(1,1) -Bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane), and bisphenol BPZ(1,1-Bis(4-hydroxyphenyl)-cyclohexane) may be at least one selected from the group consisting of cyclohexane).

The weight ratio of the monomer (first monomer) represented by Chemical Formula 7 to the monomer (second monomer) represented by Chemical Formula 8 is preferably 1:10 to 10:1. When the weight ratio of the two monomers satisfies the above range, it is possible to sufficiently secure low dielectric properties and heat resistance according to the structures of alkylphenol and bisphenol.

In this case, a compound different from the first and second monomers among the alkylphenol-based monomers represented by Formula 7 or the bisphenol-based monomers represented by Formula 8 may be further included as the third monomer. As such, when the third monomer is included, the third monomer is preferably included in an amount of 0 to 20% by weight based on the total weight of the monomer.

The formaldehyde is preferably added in an amount of 1 to 10 moles based on 1 mole of the mixture of the monomer represented by Formula 7 and the monomer represented by Formula 8. If it exceeds the above range, unreacted formaldehyde is present in a large amount, which is undesirable from an environmental point of view. Adjust appropriately within the range.

The catalyst may use a basic catalyst, for example, may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate and amines.

Preferably, the catalyst is added in an amount of 1 to 15 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the monomer represented by Formula 7 and the monomer represented by Formula 8. If the content of the catalyst exceeds 15 parts by weight, the unreacted catalyst may remain in the product to inhibit the reaction in a subsequent step or reduce the physical properties of the prepared polymer, and when used in less than 1 part by weight, the reaction rate and a problem that the yield is not sufficient, it is appropriately adjusted within the above range.

In the present invention, the reaction of step S1 is preferably carried out at 40 ~ 150 ℃ for 1 ~ 10 hours. When the reaction temperature is less than 40 ℃, there is a problem that the reaction time is long, and if it exceeds 150 ℃, the monomer causes a self-polymerization reaction and it is difficult to prepare a copolymer, so it is appropriately adjusted within the above range.

When the catalyst remains after step S1, a self-polymerization reaction of the polymer having a hydroxymethyl group may occur, and the reaction in step S3 may be inhibited by generating a salt with the phosphorus compound represented by Formula 9, so that the final product There is a problem in that the yield is lowered. In addition, when the catalyst is present in the non-halogen flame retardant polymer as the final product, it may be the main cause of deterioration of physical properties, such as low flame retardant effect, low impregnation effect, and poor compatibility with other polymers.

In order to overcome the above problems, it is preferable to perform a process of removing the catalyst after the reaction of step S1 is completed. In one embodiment of the present invention, the basic catalyst is neutralized using sulfuric acid, nitric acid, phosphoric acid aqueous solution, etc. in step S2 and the residual catalyst and formaldehyde are removed through a number of water washing processes, but the present invention is not limited thereto. can be removed.

(2) Step S2

Step S2 is a step to prepare a secondary polymer by reacting the primary polymer prepared in step S1 with a C1 to C12 alcohol. In this step, the hydroxymethyl group (-CH ₂ -OH) present in the benzene ring of the polymer is converted to an alkoxymethyl group (-CH _{2 -OR).} As described in step S1, in step S2, an acid addition and washing process for removing the catalyst in step S1 may be performed together.

Since the primary polymer having a hydroxymethyl group has very high reactivity, it is easy to self-polymerize at a temperature above room temperature. In particular, the self-polymerization occurs rapidly under a base or acid catalyst. Since the phosphorus compound represented by Chemical Formula 9 has a phosphine structure and is acidic, when the compound of Chemical Formula 9 is directly added to the primary polymer solution, the reaction between the primary polymer and the compound of Chemical Formula 9 does not occur 1 A self-condensation reaction occurs between the tea polymers, and the desired polymer cannot be obtained.

In the present invention, by performing step S2 of adding alcohol to the primary polymer after step S1, self-polymerization of the primary polymer is prevented.

At this time, the C1 to C12 alcohol used is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, glycol, 2-methoxyethanol, propylene glycol monomethyl ether, and phenol. It may be at least one selected from the group, and butanol is preferably used.

The primary polymer and the C1 to C12 alcohol are preferably reacted at 80 to 130° C. for 5 to 100 hours. If the reaction time is less than 5 hours, sufficient reaction does not occur and the problem of self-polymerization of the primary polymer cannot be solved.

At this time, it is preferable to react 10 to 1000 parts by weight of the polymer with respect to 100 parts by weight of the alcohol. If the polymer is added in an amount of less than 10 parts by weight, the yield of the final product per batch may cause a problem that productivity is significantly reduced, and if it exceeds 1000 parts by weight, the equivalent of alcohol required for the reaction may not be reached. Since it is not possible to secure the above-mentioned effect, it is appropriately adjusted within the above range.

After the reaction for preparing the secondary polymer is completed, a step of removing unreacted residual formaldehyde by adding an amine compound may be further performed. Residual unreacted formaldehyde easily reacts with the phosphorus compound represented by Formula 9 even in the absence of a catalyst, and remains in the non-halogen flame-retardant polymer after the reaction to reduce flame retardancy, impregnation properties and compatibility with other polymers. . Accordingly, in the present invention, unreacted formaldehyde is removed by additionally adding an amine compound.

The amine compound is a primary amine such as metaphenylene diamine, benzoguanamine, trimethyl hexamethylene diamine, isophorone diamine, and carbonyl diamine. , N-ethylbenzylamine (N-ethylbenzylamine), bis (2-ethylhexy) amine (Bis (2-ethylhexy) amine, can be used a secondary amine such as dipropylamine (dipropylamine), preferably 1 Use a primary amine In general, formaldehyde reacts with a primary or secondary amine to produce urea, which is water-soluble, so it is easy to remove from the reaction system.

In this case, the amine compound is preferably added in an amount of 4 equivalents or less based on unreacted formaldehyde. If it exceeds the above range, the amine compound may remain in the final product, resulting in problems such as reduced heat resistance.

(3) Step S3

In step S3, the final product of the present invention is non-halogen by reacting the prepared secondary polymer with a phosphorus compound (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) represented by the following formula (9). A flame retardant polymer is prepared.

[Formula 9]

By the addition of the phosphorus compound represented by Chemical Formula 9, the final product has flame retardancy. The phosphorus compound reacts with the alkoxymethyl group of the secondary polymer to replace the alkoxy group and form a C-P bond. In this case, the ratio in which the alkoxy group of the secondary polymer is substituted with the phosphorus compound is 10 to 100%.

The compound represented by Formula 9 is added in an amount of 10 to 1000 parts by weight based on 100 parts by weight of the monomer represented by Formula 7 and the monomer represented by Formula 8. If the content of the compound represented by Formula 9 is less than 10 parts by weight, the primary polymer that does not participate in the reaction in the reaction between the secondary polymer and the alcohol undergoes a dehydrogenation reaction at a high temperature, resulting in gelation or poor flame retardancy. A problem that may deteriorate may occur, and when it exceeds 1000 parts by weight, the compound represented by Formula 9 remains as an unreacted substance in the final product copolymer, which may significantly decrease physical properties such as heat resistance of the final copolymer. problems can arise

The reaction of step S3 is preferably performed at 100 to 250 °C for 3 to 20 hours. When the above reaction conditions are satisfied, a sufficient reaction rate can be obtained and the unreacted residual amount of the compound represented by Formula 9 can be minimized.

Flame Retardant Polymer Composition

The present invention provides a flame retardant polymer composition comprising an epoxy resin, an epoxy curing agent, a curing accelerator and a non-halogen flame retardant polymer according to the present invention.

The epoxy resin is not particularly limited in the present invention, and those used in the art may be used without limitation. Non-limiting examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, Alicyclic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional phenol type epoxy resin, Biphenyl novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol phenol coaxial novolak type epoxy resin, naphthol choresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type There are epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins, and these may be used alone or in combination of two or more types.

The epoxy curing agent may be used without any particular limitation as long as it is a conventional curing agent known in the art as a curing reaction capable of proceeding with an epoxy resin. For example, an amine curing agent, an acid anhydride curing agent, an isocyanuric acid curing agent, a phenol-based curing agent, etc. may be used, and these may be used alone or in combination of two or more.

The amine curing agent includes dicyandiamide, diethylenetriamine, tetraethylenetriamine, tetraethylenepentaamine, isopropyldiamine, bis(aminomethyl)cyclohenic acid, 1,4-butanediol bis(3-aminopropyl)ether, xylenediamine, 1,4-phenylenediamine, or the like can be used.

Acid anhydride curing agents include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethyl glutaric anhydride, Diethyl glutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like can be used.

As the isocyanuric acid curing agent, 1,3,5-tris(1-carboxymethyl)isocyanurate, 1,3,5-tris(2-carboxyethyl)isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, 1, 3-bis (2-carboxyethyl) isocyanurate, etc. are mentioned.

Phenolic curing agents include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and/or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and form a novolak-type phenol resin obtained by condensing or co-condensing a compound having an aldehyde group, such as aldehyde, benzaldehyde, and salicylaldehyde, under an acidic catalyst; phenol/aralkyl resin synthesized from phenols and/or naphthols and dimethoxyparaxylene or bis(methoxy)biphenyl; aralkyl-type phenol resins such as biphenylene-type phenol/aralkyl resins and naphthol/aralkyl resins; dicyclopentadiene type phenol resins such as dicyclopentadiene type phenol novolac resin and dicyclopentadiene type naphthol novolac resin synthesized by copolymerization of phenols and/or naphthols with dicyclopentadiene; triphenylmethane type phenol resin; terpene-modified phenolic resin; para-xylene and/or meta-xylene-modified phenolic resins; melamine-modified phenolic resin; Alternatively, a cyclopentadiene-modified phenol resin may be used.

In addition, other epoxy curing agents such as isocyanate-based, mercaptan-based, and melamine may be used.

The curing accelerator is a material that promotes the reaction between the epoxy resin and the curing agent, and for example, an imidazole-based curing accelerator, an amine-based curing accelerator, and a metal-based curing accelerator, but is not limited thereto.

Non-limiting examples of the imidazole-based curing accelerator that can be used include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hexylimidazole, 2-isopropyl Imidazole, 2-undecyl imidazole, 2-heptanedecyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2 -Methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl-2-phenyl imidazole trimellitate, 2,4-diamino-6-(2'-methylimidazole-(1')-ethyl-s-triazine, 2-pecyl-4,5-dihydroxymethylimidazole; 2-Pesyl-4-methyl-5-hydroxymethylimidazole, 2-pecyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2-ethyl-5- methylimidazole), 2-aminoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxy methyl) imidazole, 1-dodecyl-2-methyl -3-benzylimidazolinium chloride, imidazole-containing polyamide, mixtures thereof, etc. In addition, tertiary amines, organometallic compounds, organophosphorus compounds, boron compounds, etc. may be additionally used.

Non-limiting examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine; amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecel (DBU), or and mixtures of one or more thereof.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, zinc(II) acetylacetonate, and the like. an organic zinc complex, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. not limited Examples of the organometallic salt include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. The metal-based curing accelerator as described above may be used alone or in combination of two or more.

The flame retardant polymer composition according to the present invention preferably contains 30 to 70 parts by weight of the epoxy curing agent, 0.1 to 1 parts by weight of the curing accelerator, and 10 to 150 parts by weight of the non-halogen flame retardant polymer based on 100 parts by weight of the epoxy resin. do. If the non-halogen flame-retardant polymer is included in an amount of less than 10 parts by weight based on 100 parts by weight of the epoxy resin, there is a problem that flame retardancy cannot be ensured due to insufficient phosphorus content in the entire formulation, and when it exceeds 150 parts by weight, the reactivity is There is a problem of lowering and lowering solubility with other resins.

The non-halogen flame-retardant polymer according to the present invention has low dielectric properties due to its alkylphenol structure, excellent heat resistance due to its bisphenol structure, and excellent flame retardancy with a phosphorus content of 5 to 12% by weight. Therefore, the flame-retardant polymer composition comprising the non-halogen flame-retardant polymer according to the present invention is excellent as an additive of engineering plastics such as polycarbonate, acrylonitrile butadiene styrene (ABS), and high impact polystyrene (HIPS). It has flame retardancy, heat resistance, and physical and chemical properties, and can be used as a raw material for epoxy resins, cyanate resins and acrylate resins, and as a curing agent for epoxy resins. Therefore, the flame-retardant polymer composition according to the present invention is an insulating material for high-reliability electric and electronic components such as an epoxy molding compound (EMC), a halogen-free compound, and a printed circuit board (PCB) requiring excellent flame retardancy and thermal stability; It can be widely applied to various composite materials such as insulating plates, adhesives, coatings, and paints.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that changes and modifications fall within the scope of the appended claims.

Example One

At room temperature, 320 g of PTBP (P-tertiary butyl phenol), 80 g of BPA (4,4-Dihydroxy-2,2-diphenyl propane), 531.3 g of 40% formaldehyde aqueous solution and 24 g of 50% sodium hydroxide aqueous solution were put into the reactor. Then, it was heated and reacted with stirring at 80 °C for 4 hours. Thereafter, degassing at a vacuum degree of 40 Torr or less up to 70 ° C, 300 g of butanol was added, and then 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst, and the alcohol was added while draining the water produced at 110 ° C. for 20 hours. carried out. After completion of the reaction, 210 g of water and 60 g of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water twice more by 100 g of water. 575 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) was added to the resin layer and reacted at 130 for 20 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, 1100 g of a solid copolymer was obtained by degassing under reduced pressure.

The obtained non-halogen flame retardant polymer was measured for phosphorus content and molecular weight through US EPA 3052 and gel permeation chromatograph (GPC). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.7% and a molecular weight of 712 g/mol. In addition, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphate-2-oxide present at ^{2385 cm -1 was} It was observed to decrease with reaction time (FT-IR results: Phenol-like hydroxygroup: 3247 cm ^-1 , P=O: 1199/ 1280 cm ^-1 , PO-Ph: 972 cm ^-1 , PC (aliphatic C)) 1431 cm ^-1 ).

Example 2

At room temperature, 240 g of PTBP (P-tertiary butyl phenol), 160 g of BPA (4,4-Dihydroxy-2,2-diphenyl propane), 562.9 g of 40% formaldehyde aqueous solution and 24 g of 50% sodium hydroxide aqueous solution were put into the reactor. Then, it was heated and reacted with stirring at 80 °C for 4 hours. Thereafter, degassing at a vacuum degree of 40 Torr or less up to 70 ° C, 300 g of butanol was added, and then 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst, and the alcohol was added while draining the water produced at 110 ° C. for 20 hours. carried out. After completion of the reaction, 210 g of water and 60 g of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water twice more by 100 g of water. 575 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) was added to the resin layer and reacted at 130 for 20 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, 1130 g of a solid copolymer was obtained by degassing under reduced pressure.

The non-halogen flame retardant polymer thus obtained was measured for phosphorus content and molecular weight through US EPA 3052 and gel permeation chromatograph (GPC). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.8% and a molecular weight of 821 g/mol. In addition, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphate-2-oxide present at ^{2385 cm -1 was} It was observed to decrease with reaction time (FT-IR results: Phenol-like hydroxygroup: 3247 cm ^-1 , P=O: 1199/ 1280 cm ^-1 , PO-Ph: 972 cm ^-1 , PC (aliphatic C)) 1431 cm ^-1 ).

Example 3

At room temperature, 160 g of PTBP (P-tertiary butyl phenol), 240 g of BPA (4,4-Dihydroxy-2,2-diphenyl propane), 594.5 g of 40% formaldehyde aqueous solution and 24 g of 50% sodium hydroxide aqueous solution were put into the reactor. Then, it was heated and reacted with stirring at 80 °C for 4 hours. Thereafter, degassing at a vacuum degree of 40 Torr or less up to 70 ° C, 300 g of butanol was added, and then 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst, and the alcohol was added while draining the water produced at 110 ° C. for 20 hours. carried out. After completion of the reaction, 210 g of water and 60 g of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water twice more by 100 g of water. 575 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) was added to the resin layer Then, the reaction mixture was reacted at 130 °C for 20 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, 1090 g of a solid copolymer was obtained by degassing under reduced pressure.

The obtained non-halogen flame retardant polymer was measured for phosphorus content and molecular weight through US EPA 3052 and gel permeation chromatograph (GPC). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.6% and a molecular weight of 1031 g/mol. In addition, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphate-2-oxide present at ^{2385 cm -1 was} It was observed to decrease with reaction time (FT-IR results: Phenol-like hydroxygroup: 3247 cm ^-1 , P=O: 1199/ 1280 cm ^-1 , PO-Ph: 972 cm ^-1 , PC (aliphatic C)) 1431 cm ^-1 ).

comparative example One

At room temperature, 600 g of PTBP (P-tertiary butyl phenol), 898 g of 40% formaldehyde aqueous solution and 24 g of 50% aqueous sodium hydroxide solution were put into the reactor, and then heated and reacted with stirring at 80 for 5 hours. Thereafter, degassing at a vacuum degree of 40 Torr or less to 70° C., 888 g of butanol was added, and then 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst, and the alcohol was added while draining the water generated at 110° C. for 20 hours. carried out. After completion of the reaction, 300 g of water and 45 g of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde had been removed was separated and washed with water twice more by 200 g of water. 507 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) was added to the resin layer and reacted at 130 for 20 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, 1043 g of a solid polymer was obtained by degassing under reduced pressure.

The obtained polymer was measured for phosphorus content and molecular weight through US EPA 3052 and GPC (gel permeation chromatograph). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.7% and a molecular weight of 720 g/mol. In addition, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphate-2-oxide present at ^{2385 cm -1 was} disappeared (FT-IR results: Phenol-like hydroxygroup: 3247 cm ^-1 , P=O: 1199/1280 cm ^-1 , PO-Ph: 972 cm ^-1 , PC (aliphatic C) 1431 cm ^-1 .

comparative example 2

At room temperature, 228 g of BPA (4,4-dihydroxy-2,2-diphenyl propane), 300 g of 40% formaldehyde aqueous solution and 8 g of 50% sodium hydroxide aqueous solution were put into the reactor, and then heated and reacted with stirring at 70 for 5 hours. made it Thereafter, degassing at a vacuum degree of 40 Torr or less to 70 ° C, 300 g of butanol was added, and then 5 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst, and the alcohol was added while draining the water generated at 110 ° C. for 10 hours. carried out. After completion of the reaction, 250 g of water and 60 g of carbonyl diamine were added to the reactor to remove unreacted formaldehyde and washed with water. The resin layer of the upper layer from which unreacted formaldehyde was removed was separated and washed with water twice more by 100 g of water. 540 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) was added to the resin layer and reacted at 170 for 12 hours while removing butanol and water present in the reaction mixture. After completion of the reaction, 752 g of solid was obtained by degassing under reduced pressure.

The obtained polymer was measured for phosphorus content and molecular weight through US EPA 3052 and gel permeation chromatograph (GPC).

As a result, it was confirmed that the obtained polymer had a phosphorus content of 9.2% and a molecular weight of 1410 g/mol. In addition, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphate-2-oxide present at ^{2385 cm -1 was} disappeared (FT-IR results: Phenol-like hydroxygroup: 3247 cm ^-1 , P=O: 1199/1280 cm ^-1 , PO-Ph: 972 cm ^-1 , PC (aliphatic C) 1431 cm ^-1 .

Experimental example One

The following experiments were performed on the polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 2 above.

(1) Molecular weight measurement

The polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 2 were dissolved in tetrahydrofuran (THF) at a concentration of 4000 ppm, and gel permeation chromatography (GPC (0 to 100,000 g/mol) was performed. was used to measure the weight average molecular weight.

(2) Measurement of phosphorus content

The phosphorus content of the polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 2 is in US EPA 3052 (Intertec Testing Services Korea Ltd. survey, With reference to US EPA 3052, by acid digestion and determined by ICP-OES). investigated by The phosphorus content of the varnish was analyzed through calculation.

(3) varnish manufacturing

Using the polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 2, varnishes were prepared in the formulation shown in Table 1 below. At this time, as the phenol novolac hardener, phenol novolac (PN) resin (KPH-2004, Kolon Industries Co., Ltd.) having a hydroxyl equivalent weight of 106, Mn = 1200 (n = 11 to 12), and a softening point of 120 was used. , Phenol Novolac Epoxy resin used an equivalent weight of 184 g/mol (KEP-1138, Kolon Industries Co., Ltd.), and 2-ethyl-4-methyl-imidazole (2-Ethyl-4-methyl) was used as a curing accelerator. imidazole, 2E4MZ) was used at 0.4 phr compared to the solid epoxy resin.

(4) Preparation of prepregs

The varnish prepared in (2) was impregnated with glass fibers, dried naturally at room temperature for 1 hour, and then dried in an oven at 155 for 5 minutes to prepare a prepreg.

(5) Manufacture of copper clad laminate

The 8 layers of the prepreg prepared in (3) were made of copper foil (1 once) on the front and back, and ^{pressed at 195 at 40 kgf/cm 2} under pressure for 120 minutes.

(6) DSC {(Differential Scanning Calorimeters; Differential Scanning Calorimeters) measurement

Measurements were made at a temperature increase rate of 20 per minute at 30-250 using a TA Instruments DSC Q2000.

(8) Measurement of dielectric properties (Dk/Df)

After the copper clad laminate prepared in (4) was cut to 1 cm × 1 cm, the copper foil was peeled off and the dielectric constant (Dk) and dielectric loss (Df) under 1 GHz were measured using an Agilent E4991 RF Impedance/Material Analyzer.

(9) flame retardancy measurement

It was measured by the UL-94 method.

The physical properties measured by the above method are shown in Table 1 below.

Item Example comparative example One 2 3 One 2 varnish
Produce Flame Retardant Polymer (g) 100 100 100 100 100 Phenol Novolac Hardener (g) 100 100 100 100 100 Phenol Novolac Epoxy (g) 200 200 200 200 200 2E4MZ(g)* 0.28 0.28 0.28 0.28 0.28 1-methoxy-2-propanol (g) 171.4 171.4 171.4 171.4 171.4 Varnish solids content (wt%) 70 70 70 70 70 Phosphorus content in varnish (wt%) 2.24 2.23 2.25 2.21 2.30 Glass transition temperature (℃) 170.4 171.3 173.1 160.4 175.3 Dk (@1GHz) 3.10 3.12 3.15 3.08 3.45 Df (@1GHz) 0.009 0.010 0.013 0.008 0.018 Flame retardant (UL-94) V-0 V-0 V-0 V-0 V-0

As shown in Table 1, the copolymers prepared in Examples 1 to 3 exhibited lower dielectric constant and dielectric loss values compared to Comparative Example 2, which is a BPA homopolymer.

On the other hand, the copolymers of Examples 1 to 3 all showed a high glass transition temperature of 170 ° C. or higher, which was higher than that of Comparative Example 1, which was a PTBP homopolymer.

Since the non-halogen flame retardant polymer according to the present invention contains both an alkylphenol-based compound exhibiting low dielectric properties due to an alkyl group and a bisphenol-based compound exhibiting high heat resistance due to a molecular structure with low fluidity, the low dielectric properties as described above and a high glass transition temperature.

In addition, the non-halogen flame retardant polymer of the present invention has a phosphorus content of 5 to 12% by weight, indicating a flame retardancy of V-0 grade.

As described above, since the halogen-free flame retardant polymer according to the present invention exhibits excellent flame retardancy, low dielectric properties and high glass transition temperature, it can be applied to high-speed signal transmission and high-frequency region signal transmission, and printed circuit boards requiring heat resistance, It can be widely applied to various composite materials such as insulating plates, adhesives, coatings, and paints.

Claims (12)

A non-halogen flame retardant polymer comprising two or more repeating units selected from the following Chemical Formulas 1 to 4, at least one of the repeating units of Chemical Formulas 1 and 3, and at least one or more of the repeating units of Chemical Formulas 2 and 4 :
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,
X ₁ is

and X ₂ is

In this case, R ₁ is H or a C1 to C5 alkyl group, R ₂ is a C1 to C12 alkoxy group, and R ₂ is at least one alkoxy group in the polymer.

substituted with, R ₃ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, Z ₁ is SO, SO ₂ , or a C1 to C12 alkylene group,
a, b, c, and d are each an integer of 1 or more and 10 or less) According to claim 1,
The R ₁ is a t-butyl group, R ₂ is a butoxy group, and the butoxy group of R ₂ is at least one or more in the polymer.

is substituted with, R ₃ is H, and Z ₁ is —C(CH ₂ ) ₂ —. According to claim 1,
The non-halogen flame retardant polymer is a non-halogen flame retardant polymer, characterized in that the weight average molecular weight is 500 ~ 2500 g / mol. According to claim 1,
The non-halogen flame-retardant polymer is a non-halogen flame-retardant polymer, characterized in that the phosphorus content is 5 to 12% by weight. According to claim 1,
The non-halogen flame-retardant polymer is a non-halogen flame-retardant polymer, characterized in that the glass transition temperature (T _g ) is 170 ℃ or more. According to claim 1,
A non-halogen flame retardant polymer, characterized in that it further comprises at least one repeating unit selected from the following Chemical Formulas 5 and 6, wherein the content is 0 to 20% by weight based on the total weight of the polymer.
[Formula 5]

[Formula 6]

(In Formulas 5 and 6,
X ₃ is

or

In this case, R ₄ is H or a C1 to C5 alkyl group, R ₂ is a C1 to C12 alkoxy group, and the alkoxy group of R ₂ is at least one or more in the polymer.

substituted with, R ₅ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, Z ₂ is SO, SO ₂ , or a C1 to C12 alkylene group,
e and f are each an integer of 1 or more and 10 or less,
X ₃ is

When , R ₄ and R ₁ are different from each other,
X ₃ is

When , R ₅ and R ₃ are different from each other, or Z ₂ and Z ₁ are different from each other) S1) reacting a monomer represented by the following formula (7), a monomer represented by the following formula (8), and formaldehyde in the presence of a catalyst to produce a primary polymer including a hydroxymethyl group;
S2) reacting the primary polymer with a C1 to C12 alcohol to produce a secondary polymer including a benzene ring including an alkoxymethyl group; and
S3) generating a non-halogen flame retardant polymer by reacting the secondary polymer with a compound represented by the following Chemical Formula 9;
A method for preparing a non-halogen flame retardant polymer comprising:
[Formula 7]

[Formula 8]

[Formula 9]

(In Formulas 7 and 8,
R ₁ is H or a C1 to C5 alkyl group, R ₃ is H, a C1 to C6 alkyl group, or a C6 to C12 aryl group, and Z ₁ is SO, SO ₂ , or a C1 to C12 alkylene group) 8. The method of claim 7,
The monomers represented by Formula 8 include bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol BPZ. A method for producing a non-halogen flame retardant polymer, characterized in that at least one selected from the group consisting of. 8. The method of claim 7,
The catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, and a method for producing a non-halogen flame retardant polymer, characterized in that at least one selected from the group consisting of amines. 10. A non-halogen flame retardant polymer prepared by the method of any one of claims 7 to 9. an epoxy resin, an epoxy curing agent, a curing accelerator and a non-halogen flame retardant;
The flame retardant polymer composition, characterized in that the non-halogen flame retardant is a copolymer according to any one of claims 1 to 6. 12. The method of claim 11,
The flame retardant polymer composition comprises 30 to 70 parts by weight of the epoxy curing agent, 0.1 to 1 parts by weight of the curing accelerator, and 10 to 150 parts by weight of the non-halogen flame retardant polymer based on 100 parts by weight of the epoxy resin. polymer composition.