KR20180001281A - 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 copolymer, a preparation method for the same, and a non-halogen flame retardant composition comprising the same. Specifically, the present invention relates to a polymer exhibiting desirable flame retardant properties, low dielectric properties, and a glass transition temperature (Tg) of 150C or more and less than 170C; to a preparation method for the same; and to a non-halogen flame retardant composition comprising the same. According to the present invention, the non-halogen flame retardant polymer exhibits desirable flame retardant properties, low dielectric properties, and a glass transition temperature of 150C or more and 170C or less by comprising as monomers an alkyl phenol compound having low dielectric constant and dielectric loss, and a bisphenol compound having good heat resistance. Thus, the copolymer according to the present invention may be used as an electrical insulation material for transmitting high-speed signals in high-frequency areas.

Description

TECHNICAL FIELD [0001] The present invention relates to a non-halogen flame retardant polymer, a method for producing the same, and a flame retardant polymer composition containing the same,

The present invention relates to a non-halogen flame retardant copolymer, a method for producing the same, and a non-halogen flame retardant composition containing the same. More particularly, the present invention relates to a flame retardant composition having excellent flame retardancy, low dielectric constant, and glass transition temperature (Tg) , A process for producing the same, and a non-halogen flame retardant composition containing the same.

In recent years, due to miniaturization and high functionality of electronic devices, the wiring width of circuits has become narrow and the number of component mounting has increased. Materials having heat resistance and flame retardancy are widely used as materials for substrates and parts in order to ensure safety against fire when such electronic equipment is used.

In addition, the frequency band of signals used in communication electronic devices is shifting from the MHz range to the GHz range. In order to improve the signal transmission rate in the high frequency region and reduce the noise, the dielectric constant of the material used for the substrate and the components of the device needs to be low.

Epoxy resins are widely used as materials satisfying these requirements. Epoxy resins are widely used in the fields of electric and electronic materials, adhesives, paints, and the like due to their high heat resistance, dimensional stability, high adhesive properties, excellent chemical resistance and electrical characteristics.

As a technique for imparting flame retardancy to such an epoxy resin, there is a technique of reacting a halogen-containing compound such as tetrabromobisphenol A at the time of synthesizing an epoxy resin, or adding a halogen-containing compound in the epoxy resin composition state. However, the halogen-based flame-retardant curing agent has a problem that toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated during combustion, and the use thereof is limited recently.

Therefore, it is necessary to develop a new non-halogen flame retardant compound having flame retardancy without containing halogen, having excellent heat resistance and low dielectric property suitable for high frequency signal transmission.

Korean Patent Laid-Open Publication No. 2016-0051085, Non-Halogen-Based Flame Retardant Polymer and Method for Producing the Same

The present inventors have found that a copolymer produced by copolymerizing an alkylphenol compound exhibiting low dielectric properties and a bisphenol compound having excellent heat resistance and having excellent flame retardance characteristics, low dielectric properties, and glass having a temperature of 150 ° C or more and less than 170 ° C Transition temperature (Tg), thereby completing the present invention.

Accordingly, an object of the present invention is to provide a halogen-free flame retardant polymer which exhibits excellent flame retardancy, intermediate range of glass transition temperature and low dielectric constant, without halogen.

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

Still another object of the present invention is to provide a non-halogen flame retardant polymer composition containing the above-mentioned non-halogen flame retardant polymer.

In order to attain the above object, the present invention provides a resin composition comprising at least one of repeating units represented by the following formulas (1) and (2), at least one repeating unit selected from the following formulas At least one non-halogen flame retardant polymer, and a flame retardant polymer composition comprising the same:

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 1 to 4,

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

In addition,

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

S2) reacting the primary polymer with an alcohol of C1 to C12 to produce a secondary polymer containing an alkoxymethyl group; And

S3) reacting the secondary polymer with a compound represented by the following formula (9) to produce a non-halogen flame retardant polymer;

Halogenated flame retardant polymer comprising the steps of:

 (7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the above formulas (7) and (8)

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

The copolymer according to the present invention comprises an alkylphenol compound having a low dielectric constant and a low dielectric loss rate and a bisphenol compound having excellent heat resistance as a unit, and has excellent flame retardancy, low dielectric constant, and glass transition temperature (Tg) . Accordingly, 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 the high-frequency range for mid-Tg, a smart phone, and an automotive application.

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

Non-halogen flame retardant polymer

The present invention relates to a resin composition comprising a resin composition comprising at least one of repeating units represented by the following formulas (1) and (2), at least one repeating unit selected from the following formulas (1) Halogen flame retardant polymer.

The repeating units may be arranged in various forms such as a ramdom, an alternating, and a block.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 1 to 4,

이고, X₂는

이며, 이때 R₁은 C6 내지 C10의 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

, Wherein R ₁ is a C 6 to C 10 alkyl group, R ₂ is a C 1 to C 12 alkoxy group, and the alkoxy group of R ₂ is at least one

, R ₃ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, Z ₁ is SO, SO ₂ , a C 1 to C 12 alkylene group,

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

The C1 to C10 alkyl groups referred to in this specification may be straight-chain or branched. Specifically, the linear alkyl group means a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group, and the branched alkyl group is one of the straight- Means that at least hydrogen is substituted with a methyl group, an ethyl group, a propyl group, or a butyl group.

The C1 to C12 alkoxy groups referred to in the present specification include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentoxy, Hydroxyethoxy group, 2-methoxyethoxy group, 3-methoxypropoxy group, or phenoxy group.

The C6 to C12 aryl group referred to in the present specification may be a phenyl group substituted or unsubstituted with a C1 to C6 alkyl group.

The C1 to C12 alkylene groups referred to in the present specification include - (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 a C6 to C11 aryl Substituted or unsubstituted structure. The C6 to C10 aryl group may be included between the CC bonds of the - (CH ₂ ) _n - basic skeleton.

가 혼재할 수 있는데, 공중합체는 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, the R ₂ may be different in each repeating unit or in the repeating unit. That is, the copolymer contains an alkoxy group

May be mixed, wherein the copolymer comprises at least one

By having a substituent, flame retardant properties can be exhibited. Specifically, in the non-halogen flame retardant polymer of the present invention,

Is in the range of 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 comonomers.

(7)

[Chemical Formula 8]

(In the above formulas (7) and (8)

R ₁ is a C 6 to C 10 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 the general formula (7), R ₁ is preferably a butyl group, a pentyl group or a hexyl group substituted by 2 to 4 methyl groups, more preferably a t-octyl group.

R 8 in the formula ₃ is to preferably H, Z is -CH ₂ to preferred _{-, -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 ) -, and more preferably -C (CH ₂ ) ₂ -.

The alkylphenol compound of formula (7) is suitable as an electrical insulating material in the high frequency region because the free volume of the cured product after curing becomes large due to the alkyl group and exhibits low dielectric constant and dielectric loss factor. However, when a polymer is prepared only with the compound of the formula (7), heat resistance is poor. Thus, in the present invention, a non-halogen flame retardant polymer having a glass transition temperature of 150 ° C or more and less than 170 ° C is obtained by preparing a polymer using a bisphenol-based compound having a high glass transition temperature as a comonomer.

As described above, the non-halogen flame retardant polymer according to the present invention necessarily contains one of the alkylphenol compounds represented by the general formula (7) as the first monomer and one of the bisphenol compounds represented by the general formula (8) as the second monomer, In addition, it may further comprise one of the alkylphenol-based or bisphenol-based compounds different from the first monomer and the second monomer as the third monomer. In this case, the polymer further includes at least one repeating unit selected from the following formulas (5) and (6).

[Chemical Formula 5]

[Chemical Formula 6]

(In the above formulas 5 and 6,

또는

이며, 이때 R₄는 C6 내지 C10의 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

, Wherein R ₄ is a C 6 to C 10 alkyl group, R ₂ is a C 1 to C 12 alkoxy group, and the alkoxy group of R ₂ is at least one

, R ₅ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, Z ₂ is SO, SO ₂ , a C 1 to C 12 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

, 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

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

At this time, the repeating units of the formulas (5) and (6) are 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. When the weight average molecular weight is less than 500 g / mol, there is a problem that the heat resistance is lowered. When the weight average molecular weight exceeds 2500 g / mol, there is a problem that impregnation is poor.

The non-halogen flame retardant polymer according to the present invention preferably contains phosphorus in an amount of 5 to 12 wt% to ensure flame retardant properties. If the phosphorus content is less than 5% by weight, the flame retardant effect is insufficient and a large amount of flame retardant auxiliary agent is required in the resin blending. When the phosphorus content is more than 12% by weight, the reactivity is lowered and the solubility with other resins is lowered.

Nonhalogen  Method for producing flame retardant polymer

The present invention

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

S2) reacting the primary polymer with an alcohol of C1 to C12 to produce a secondary polymer comprising a benzene ring containing an alkoxymethyl group; And

S3) reacting the secondary polymer with a compound represented by the following formula (9) to produce a non-halogen flame retardant polymer;

Halogenated flame retardant polymer comprising the steps of:

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the above formulas (7) and (8)

R ₁ is a C 6 to C 10 alkyl group, R ₃ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, and Z ₁ is an SO, SO ₂ or C 1 to C 12 alkylene group)

The method for producing a flame-retardant polymer according to an embodiment of the present invention can be represented by the following reaction formula (1).

[Reaction Scheme 1]

로 치환된다)(In the above Reaction Scheme 1, R ₂ is a C1 to C12 alkoxy group, and the alkoxy group of R ₂ is at least one

≪ / RTI >

Hereinafter, each step will be described in detail.

(1) Step S1

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

The monomer represented by the formula (7) is an alkyl phenol-based monomer, preferably POP (p-tert-octyl phenol).

Examples of the monomer represented by the formula (8) include bisphenol-based monomers such as 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, bis- (4-hydroxyphenyl) diphenylmethane and bisphenol C (2,2-bis (3-methyl-4-hydroxyphenyl) propane Bis (4-hydroxyphenyl) methane, bisphenol G (2,2-bis (4-hydroxy-3-isopropyl-phenyl) propane Bis (4-hydroxyphenyl) sulfone, bisphenol P (1,4-bis (2- (4-hydroxyphenyl) 4-hydroxyphenyl) -2-propyl) benzene, bisphenol PH (5,5 '- (1-Methylethyliden) Bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, and bisphenol BPZ (1,1-bis (4-hydroxyphenyl) -cyclohexane).

Here, the weight ratio of the monomer (first monomer) represented by Formula 7 to the monomer (second monomer) represented by Formula 8 is preferably 1:10 to 10: 1. When the weight ratio of the two monomers satisfies the above range, low dielectric properties and heat resistance according to the structure of alkylphenol and bisphenol can be sufficiently secured.

Here, the third monomer may further include a compound different from the first and second monomers among the alkylphenol monomer represented by formula (7) or the bisphenol monomer represented by formula (8). As such, when the third monomer is included, it is preferable that the third monomer is contained in an amount of 0 to 20% by weight based on the total weight of the monomers.

The formaldehyde is preferably added in an amount of 1 to 10 moles per 1 mole of the mixture of the monomer represented by the formula (7) and the monomer represented by the formula (8). If the amount exceeds the above range, unreacted formaldehyde is present in a large amount, which is undesirable from an environmental point of view. If the amount is less than the above range, the content of the hydroxymethyl group of the polymer is reduced and the yield of the final product is lowered. Adjust properly within the range.

The catalyst 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.

The catalyst is added in an amount of preferably 1 to 15 parts by weight, more preferably 2 to 8 parts by weight based on 100 parts by weight of the total of the monomer represented by the general formula (7) and the monomer represented by the general formula (8). If the content of the catalyst is more than 15 parts by weight, the unreacted catalyst may remain in the product to inhibit the reaction of the subsequent step or lower the physical properties of the produced polymer. If the content of the catalyst is less than 1 part by weight, And the yield becomes insufficient, so that it is appropriately controlled within the above range.

In the present invention, the reaction of Step S1 is preferably carried out at 40 to 150 DEG C for 1 to 10 hours. If the reaction temperature is lower than 40 ° C., the reaction time may become longer. If the reaction temperature is higher than 150 ° C., the monomer may undergo an autopolymerization reaction, making it difficult to produce a copolymer.

If the catalyst remains after the step S1, it is possible to cause an autopolymerization reaction of the polymer having a hydroxymethyl group, and a phosphorus compound represented by the formula (9) and a salt thereof can be produced, thereby inhibiting the reaction in the step S3. The yield is lowered. In addition, when the catalyst is present in a non-halogen flame retardant polymer as a final product, it may be a 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-described problem, it is preferable to carry out the step 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 or the like in step S2, and the remaining catalyst and formaldehyde are removed through a plurality of washing steps. However, the present invention is not limited thereto, Can be removed.

(2) Step S2

S2 is a step by the first polymer to react with a C1 to C12 alcohol produced in step S1 secondary hydroxymethyl groups (-CH ₂ -OH) to a step of producing a polymer, present in the benzene ring of the polymer at this stage Is converted to an alkoxymethyl group (-CH ₂ -OR). As described in step S1, in step S2, the addition of acid and the washing step for removing the catalyst in step S1 may be performed together.

Since the primary polymer having a hydroxymethyl group is highly reactive, it is likely to undergo autopolymerization at a temperature higher than room temperature. In particular, the autocopolymerization takes place rapidly in the presence of a base or an acid catalyst. Since the phosphorus compound represented by the general formula (9) has a phosphine structure and exhibits acidity, when the compound of the general formula (9) is added directly to the primary polymer solution, the reaction between the primary polymer and the compound of the general formula (9) An autocondensation reaction takes place between the tertiary polymers, and a desired polymer can not be obtained.

In the present invention, the step (S2) of adding an alcohol to the primary polymer after the step (S1) is performed to prevent the autopolymerization reaction of the primary polymer.

The C1 to C12 alcohols to be used herein may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, glycol, 2-methoxyethanol, propylene glycol monomethyl ether, , And preferably butanol is used.

The primary polymer and the C1 to C12 alcohols are preferably reacted at 80 to 130 DEG C for 5 to 100 hours. If the reaction time is less than 5 hours, sufficient reaction does not occur and the self-polymerization problem of the primary polymer can not be solved. If the reaction time exceeds 100 hours, the productivity may be significantly decreased due to the prolongation of the process time.

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 be small, resulting in a problem of poor productivity. If the amount of the polymer is more than 1000 parts by weight, And the above-mentioned effect can not be ensured. Therefore, it is appropriately adjusted within the above range.

After the reaction for preparing the secondary polymer is completed, an amine compound may be added to remove remaining unreacted formaldehyde. Unreacted residual formaldehyde is liable to react with the phosphorus compound represented by the formula (9) even in the absence of a catalyst, and remains in the non-halogen flame retardant polymer after the reaction, which causes flame retardance, impregnation property and compatibility with other polymers . In the present invention, an amine compound is further added to remove unreacted formaldehyde.

The amine compound may be a primary amine such as metaphenylene diamine, benzoguanamine, trimethylhexamethylene diamine, isophorone diamine or carbonyl diamine. Secondary amines such as N-ethylbenzylamine, bis (2-ethylhexy) amine and dipropylamine can be used. Preferably, 1 In general, formaldehyde reacts with primary or secondary amines to form urea, which is readily soluble in the reaction system since it is water soluble.

At this time, the amine compound is preferably added in an amount of 4 equivalents or less based on the unreacted formaldehyde. If the amount exceeds the above range, the amine compound may remain in the final product, resulting in a problem of reduction in heat resistance and the like.

(3) Step S3

In step S3, the produced secondary polymer is reacted with a phosphorus compound (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) represented by the following general formula (9) A flame retardant polymer is prepared.

[Chemical Formula 9]

With the addition of the phosphorus compound represented by the above formula (9), the final product has flame retardancy. The phosphorus compound reacts with the alkoxymethyl group of the secondary polymer to displace the alkoxy group and produce a C-P bond. At this time, the ratio of the alkoxy group of the secondary polymer to the phosphorus compound is 10 to 100%.

The compound represented by the 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 the formula (7) and the monomer represented by the formula (8). If the content of the compound represented by the general formula (9) is less than 10 parts by weight, the primary polymer not participating in the reaction between the secondary polymer and the alcohol may undergo gelation at a high temperature, If the amount exceeds 1000 parts by weight, the compound represented by the general formula (9) may remain as an unreacted material in the final product copolymer, and the physical properties such as heat resistance of the final copolymer may be remarkably deteriorated Problems can occur

The reaction of step S3 is preferably performed at 100 to 250 DEG C for 3 to 20 hours. When the reaction conditions are satisfied, a sufficient reaction rate can be obtained and the unreacted residual amount of the compound represented by the 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 any of those used in the art can be used without limitation. Examples of the epoxy resin include, but are not limited to, 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, Alicyclic epoxy resins, alicyclic epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolak type epoxy resins, bisphenol F novolak type epoxy resins, dicyclopentadiene type epoxy resins, polyfunctional phenol type epoxy resins, Biphenyl novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol phenol coaxial novolak type epoxy resin, naphthol choleseol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type Epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene phenol adduct Eunghyeong the like epoxy resins, phenol aralkyl type epoxy resins and naphthol type epoxy resin, and Ara, these may be used alone or as a mixture of two or more.

The epoxy curing agent can be cured with an epoxy resin and can be used without any particular limitation as long as it is a conventional curing agent known in the art. For example, amine curing agents, acid anhydride curing agents, isocyanuric acid curing agents, phenolic curing agents and the like can be used, and these can be used alone or in combination of two or more.

Examples of the amine curing agent include dicyandiamide, diethylenetriamine, tetraethylenetriamine, tetraethylenepentamine, isopropyldiamine, bis (aminomethyl) cyclohexane, 1,4-butanediol bis (3-aminopropyl) Xylene diamine, 1,4-phenylenediamine, and the like.

Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, anhydrous glutaric acid, anhydrous dimethylglutaric acid, Anhydrous succinic acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like can be used.

Examples of the isocyanuric acid curing agent include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, and 1,3-bis (2-carboxyethyl) isocyanurate.

Examples of the phenol-based curing agent include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol and / or naphthols such as? -Naphthol,? -Naphthol and dihydroxynaphthalene A novolak type phenolic resin obtained by condensation or co-condensation of a compound having an aldehyde group such as aldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst; Phenol-aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxy) biphenyl; Arylene-type phenol resins such as biphenol-type phenol-aralkyl resin and naphthol-aralkyl resin; Dicyclopentadiene type phenolic resins such as dicyclopentadiene type phenol novolac resins and dicyclopentadiene type naphthol novolac resins synthesized by copolymerization of phenols and / or naphthols with dicyclopentadiene; Triphenylmethane type phenolic resin; Terpene-modified phenolic resins; Para-xylene and / or metaxylene-modified phenolic resins; Melamine modified phenolic resins; Or a cyclopentadiene-modified phenol resin can be used.

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

The curing accelerator is a substance for promoting the reaction between the epoxy resin and the curing agent, and examples thereof include, but are not limited to, an imidazole-based curing accelerator, an amine-based curing accelerator, and a metal-based curing accelerator.

Nonlimiting examples of imidazole-based curing accelerators that can be used are imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-heptylimidazole, 2- 2-heptanedimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl- Trimethylolpropane, trimellitate, 2,4-diamino-6- (2'-methylimidazole- (1 ') -ethyl-s-triazine, Methyl-5-hydroxymethylimidazole, 2-pheyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis- Methyl imide 2-methyl-2-methyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-dodecyl- Benzylimidazolinium chloride, imidazole-containing polyamide, and mixtures thereof. In addition, tertiary amines, organic metal compounds, organic phosphorus compounds, boron compounds, and the like can be further used.

Non-limiting examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; Amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and 1,8-diazabicyclo (5,4,0) -undecell (DBU) And mixtures of one or more of these.

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

The flame retardant polymer composition according to the present invention preferably comprises 30 to 70 parts by weight of the epoxy curing agent, 0.1 to 1 part 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 contained 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 can not be ensured due to insufficient phosphorus content in the entire formulation. When the amount is more than 150 parts by weight, There is a problem that the solubility with other resins is lowered.

The non-halogen flame retardant polymer according to the present invention exhibits low dielectric properties due to its alkylphenol structure, has excellent heat resistance due to its bisphenol structure, and has a phosphorus content of 5 to 12% by weight and excellent flame retardancy. Therefore, the flame retardant polymer composition containing the non-halogen flame retardant polymer according to the present invention is excellent as an additive for engineering plastics such as polycarbonate, acrylonitrile butadiene styrene (ABS), and high impact polystyrene (HIPS) Flame retardancy, heat resistance, physical and chemical properties, and can be used as a raw material for epoxy resins, cyanate resins and acrylate resins, and as curing agents for epoxy resins. Accordingly, the flame retardant polymer composition according to the present invention is an insulating material for highly reliable electric and electronic parts such as an epoxy molding compound (EMC), a halogen-free compound, 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, coating agents, and paints.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

Example  One

320 g of POP (P-tert-octyl phenol), 80 g of BPA (4,4-dihydroxy-2,2-diphenyl propane), 422.6 g of 40% aqueous formaldehyde solution and 24 g of 50% sodium hydroxide aqueous solution were added to the reactor at room temperature And the mixture was reacted while heating and stirring at 80 DEG C for 4 hours. Subsequently, degassing was carried out at a degree of vacuum of 40 Torr or lower 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. The alcohol addition reaction was performed while removing water generated at 110 ° C. for 20 hours Respectively. After the completion of the reaction, 210 g of water and 60 g of carbonyl diamine were charged into the reactor to remove and wash unreacted formaldehyde. The resin layer on the upper layer from which the unreacted formaldehyde was removed was separated, and further washed twice with 100 g of water. 495 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) And reacted for 130 to 20 hours while removing the butanol and water present in the reaction mixture. After completion of the reaction, the resultant was vacuum-degassed to obtain 1020 g of a solid copolymer.

The obtained non-halogen flame retardant polymer was measured for phosphorus content and molecular weight through US EPA 3052 and a gel permeation chromatograph (GPC). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.5% and a molecular weight of 690 g / mol. Further, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphospabe-2-oxide at 2385 cm ^-1 (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

240 g of POP (P-tert-octyl phenol), 160 g of BPA (4,4-dihydroxy-2,2-diphenyl propane), 481.4 g of 40% aqueous formaldehyde solution and 24 g of 50% sodium hydroxide aqueous solution were added to the reactor at room temperature And the mixture was reacted while heating and stirring at 80 DEG C for 4 hours. Thereafter, the reaction mixture was degassed at 70 ° C or less under a degree of vacuum of 40 Torr and 300 g of butanol was added. Then, 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst and the alcohol addition reaction was performed while removing water generated at 110 to 20 hours Respectively. After the completion of the reaction, 210 g of water and 31 g of carbonyl diamine were charged into the reactor to remove and wash unreacted formaldehyde. The resin layer on the upper layer from which the unreacted formaldehyde was removed was separated, and further washed twice with 100 g of water. To the resin layer, 512 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane- And reacted for 130 to 20 hours while removing the butanol and water present in the reaction mixture. After completion of the reaction, deaeration under reduced pressure yielded 1130 g of a solid copolymer.

The obtained non-halogen flame retardant polymer was measured for phosphorus content and molecular weight through US EPA 3052 and a 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 811 g / mol. Further, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphospabe-2-oxide at 2385 cm ^-1 (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

160 g of POP (P-tert-octyl phenol), 240 g of BPA (4,4-dihydroxy-2,2-diphenyl propane), 540 g of formaldehyde aqueous solution 40% (formaldehyde) and 24 g of 50% sodium hydroxide aqueous solution And then heated and reacted at 80 DEG C for 4 hours with stirring. Thereafter, the reaction mixture was degassed at 70 ° C or less under a degree of vacuum of 40 Torr and 300 g of butanol was added. Then, 24 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst and the alcohol addition reaction was performed while removing water generated at 110 to 20 hours Respectively. After the completion of the reaction, 210 g of water and 31 g of carbonyl diamine were charged into the reactor to remove and wash unreacted formaldehyde. The resin layer on the upper layer from which the unreacted formaldehyde was removed was separated, and further washed twice with 100 g of water. 525 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) And reacted for 130 to 20 hours while removing the butanol and water present in the reaction mixture. After completion of the reaction, the resultant was vacuum-degassed to obtain 1102 g of a solid copolymer.

The obtained non-halogen flame retardant polymer was measured for phosphorus content and molecular weight through US EPA 3052 and a gel permeation chromatograph (GPC). As a result, it was confirmed that the obtained polymer had a phosphorus content of 8.9% and a molecular weight of 914 g / mol. Further, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphospabe-2-oxide at 2385 cm ^-1 (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

400 g of POP (P-tert-octyl phenol), 657.7 g of formaldehyde aqueous solution 40% (formaldehyde) and 24 g of 50% sodium hydroxide aqueous solution were added to the reactor at room temperature, followed by heating and reacting at 80 ° C for 5 hours with stirring. Thereafter, the reaction mixture was degassed at 70 ° C or lower under a degree of vacuum of 40 Torr, 300 g of butanol was added, and 24 g of 80% phosphoric acid was added thereto to neutralize the sodium hydroxide catalyst. The alcohol addition reaction was carried out at 110 ° C for 20 hours, Respectively. After completion of the reaction, 300 g of water and 45 g of carbonyl diamine were charged into the reactor to remove and wash unreacted formaldehyde. The resin layer of the upper layer from which the unreacted formaldehyde was removed was separated, and further washed twice with 200 g of water. 677 g of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide) And reacted for 130 to 20 hours while removing the butanol and water present in the reaction mixture. After completion of the reaction, deaeration under reduced pressure yielded 1161 g of a solid polymer.

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 8.8% and a molecular weight of 791 g / mol. Further, as a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, the PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphospabe-2-oxide at 2385 cm ^-1 (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

228 g of BPA (4,4-Dihydroxy-2,2-diphenyl propane), 40 g of formaldehyde aqueous solution 40% (formaldehyde) and 8 g of 50% sodium hydroxide aqueous solution were added to the reactor at room temperature, followed by heating and stirring at 70 ° C for 5 hours Lt; / RTI > Thereafter, the reaction mixture was degassed at 70 ° C or less under a vacuum of 40 Torr and 300 g of butanol was added thereto. Then, 5 g of 80% phosphoric acid was added to neutralize the sodium hydroxide catalyst and the alcohol addition reaction was carried out while removing water generated at 110 ° C. for 10 hours Respectively. After completion of the reaction, 250 g of water and 60 g of carbonyl diamine were charged into the reactor to remove and wash unreacted formaldehyde. The resin layer on the upper layer from which the unreacted formaldehyde was removed was separated, and further washed twice with 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) And reacted at 170 for 12 hours while removing the butanol and water present in the reaction mixture. After completion of the reaction, vacuum degassing was conducted to obtain 752 g of a solid polymer.

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

As a result, it was confirmed that the obtained polymer had a phosphorus content of 9.2% and a molecular weight of 1,150 g / mol. As a result of FT-IR (Perkin Elmer, Spectrum 100) measurement, it was observed that PH Stretch absorption peak of 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxice which was present at 2385 cm ^-1 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 conducted on the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2.

(1) Molecular weight measurement

The polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were dissolved in tetrahydrofuran (THF) at a concentration of 4000 ppm and subjected to Gel Permeation Chromatography (GPC) (0 to 100,000 g / mol) To determine the weight average molecular weight.

(2) Determination of phosphorus content

 The phosphorus content of the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was measured by the method described in US EPA 3052 (Requested by Intertec Testing Servies Korea Ltd., with reference to US EPA 3052, by acid digestion and determined by ICP-OES) Respectively. The phosphorus content of the varnish was analyzed by calculation.

(3) varnish manufacturing

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

(4) Preparation of prepreg

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

(5) Production of copper clad laminate

Eight prepregs prepared in (3) above were prepared by pressing the copper foil (1 once) on the front and back sides and at a pressure of 40 kgf / cm ^{2 for} 120 minutes.

(6) DSC {(Differential Scanning Calorimeters) measurement

   ≪ / RTI > was measured using a TA Instruments DSC Q2000 at a heating rate of 20 per minute at 30-250.

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

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

(9) Measurement of flammability

   And 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 The 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 The phosphorus content in the varnish (wt%) 2.23 2.21 2.22 2.21 2.30 Glass transition temperature (캜) 152.6 156.7 162.3 145.5 175.3 Dk (@ 1 GHz) 2.92 2.95 2.99 2.87 3.45 Df (@ 1 GHz) 0.005 0.005 0.006 0.004 0.018 Flammability (UL-94) V-0 V-0 V-0 V-0 V-0

As a result of the test, the copolymers of Examples 1 to 3 exhibited a median value of a POP homopolymer and a BPA homopolymer with a glass transition temperature of 150 ° C or more and less than 170 ° C, and the dielectric properties were also found to be intermediate between the POP homopolymer and the BPA homopolymer Respectively.

Since the copolymer according to the present invention contains both an alkylphenol compound exhibiting low dielectric properties due to an alkyl group and a bisphenol compound exhibiting high heat resistance due to a low fluidity molecular structure, Of glass transition temperature.

As such, the copolymer according to the present invention exhibits excellent flame retardance, low dielectric properties and flame retardancy, and thus can be applied to high-speed signal transmission and high frequency signal transmission, and can be applied to various composite materials such as printed circuit boards and insulating plates, Coating agents, paints, and the like.

Claims (12)

A non-halogen flame retardant polymer comprising at least one or more repeating units of the following general formulas (1) and (2) and at least one repeating unit of general formulas (1) :
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 1 to 4,
X ₁ is

And X ₂ is

, Wherein R ₁ is a C 6 to C 10 alkyl group, R ₂ is a C 1 to C 12 alkoxy group, and the alkoxy group of R ₂ is at least one

, R ₃ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, Z ₁ is SO, SO ₂ , a C 1 to C 12 alkylene group,
a, b, c, and d are each an integer of 1 or more and 10 or less) The method according to claim 1,
Wherein R ₁ is a t-octyl group, R ₂ is a butoxy group, and the butoxy group of R ₂ is at least one

, R ₃ is H, and Z ₁ is -C (CH ₂ ) ₂ -. The method according to claim 1,
Wherein the non-halogen flame retardant polymer has a weight average molecular weight of 500 to 2,500 g / mol. The method according to claim 1,
Wherein the non-halogen flame retardant polymer has a phosphorus content of 5 to 12 wt%. The method according to claim 1,
The non-halogen flame retardant polymer is a non-halogen flame retardant polymer, characterized in that a glass transition temperature greater than (T _g) is from 150 to 170 ℃. The method according to claim 1,
And at least one repeating unit selected from the following general formula (5) and (6), wherein the content is 0 to 20% by weight based on the total weight of the polymer.
[Chemical Formula 5]

[Chemical Formula 6]

(In the above formulas 5 and 6,
X ₃ is

or

, Wherein R ₄ is a C 6 to C 10 alkyl group, R ₂ is a C 1 to C 12 alkoxy group, and the alkoxy group of R ₂ is at least one

, R ₅ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, Z ₂ is SO, SO ₂ , a C 1 to C 12 alkylene group,
e and f are each an integer of 1 or more and 10 or less,
X ₃ is

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

, 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) and a monomer represented by the following formula (8) with formaldehyde in the presence of a catalyst to produce a primary polymer containing a hydroxymethyl group;
S2) reacting the primary polymer with an alcohol of C1 to C12 to produce a secondary polymer comprising a benzene ring containing an alkoxymethyl group; And
S3) reacting the secondary polymer with a compound represented by the following formula (9) to produce a non-halogen flame retardant polymer;
≪ RTI ID = 0.0 > 1, < / RTI >
(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the above formulas (7) and (8)
R ₁ is a C 6 to C 10 alkyl group, R ₃ is H, a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, and Z ₁ is an SO, SO ₂ or C 1 to C 12 alkylene group) 8. The method of claim 7,
The monomer represented by the above-mentioned formula (8) is preferably selected from the group consisting of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, Wherein the fluorine-containing polymer is at least one selected from the group consisting of fluorine-containing polymers and fluorine-containing polymers. 8. The method of claim 7,
Wherein the catalyst is 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. A non-halogen flame retardant polymer produced 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 non-halogen flame retardant is the copolymer according to any one of claims 1 to 6. 12. The method of claim 11,
Wherein the flame retardant polymer composition comprises 30 to 70 parts by weight of the epoxy curing agent, 0.1 to 1 part 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.