KR102136212B1 - Flame retardant agent for resins, flame-retardant resin composition containing same, and method for producing organophosphorus compound - Google Patents

Abstract

상기 식에서, R₁, R₂, R₃ 및 R₄는 각각 독립해서 탄소수1∼8의 알킬기 또는 할로알킬기이고, Z₁ 및 Z₂는 각각 독립해서 수소원자, 메틸기 또는 에틸기이고, n은 0∼10이다.In the flame retardant for a resin containing an organophosphorus compound of the formula (I), the content of the compound of n=0 in the formula (I) below is 0.1 when the organophosphorus compound is measured by gel permeation chromatography (GPC). Flame retardant for resins having an average condensation degree (N) of 1.5 to 3.5, calculated from the content of each compound of n=0 to 10 in the following formula (I):

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or a haloalkyl group having 1 to 8 carbon atoms, Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10.

Description

Flame retardant for resins, flame retardant resin composition containing the same, and a method for producing an organic phosphorus compound TECHNICAL FIELD

The present invention relates to a flame retardant for a resin, a flame retardant resin composition containing the same, and a method for producing an organophosphorus compound. More specifically, the present invention exhibits excellent flame retardancy as a flame retardant for resins, especially as an additive type flame retardant when flame retarding polyurethane foams, and furthermore, has little change over time in its persistence and has low fogging resistance (low volatility). Flame retardant for resins mainly composed of polyphosphonate phosphate type organic phosphorus compounds having excellent volatile organic compounds (VOC) and low molecular weight monomeric compounds, and flame retardant resin compositions and organic phosphorus containing the same It relates to a method for preparing a compound.

In order to impart flame retardancy to the resin, a method of adding a flame retardant to the resin molded article is employed. Examples of the flame retardant include inorganic compounds, organic phosphorus compounds, organic halogen compounds, halogen-containing organic phosphorus compounds, and the like, and organic halogen compounds and halogen-containing organic phosphorus compounds exhibit excellent flame retardant effects. Organic phosphorus compounds, especially organic phosphoric acid esters and halogen-containing organic phosphoric acid esters, are widely used as flame retardants for which good flame retardant effects are obtained.

For such halogen-containing organic phosphoric acid esters, for example, US Patent No. 3122422 specification (Patent Document 1), Japanese Patent Publication S49-43272 (Patent Document 2), Japanese Patent Publication S56-36512 (Patent Document 3) And Japanese Unexamined Patent Publication No. H11-100391 (Patent Publication 4).

Among the various resins, the foam (polyurethane foam) of the polyurethane resin is limited in its use because it is combustible, and various studies have been conducted recently due to the flame retardancy of the polyurethane foam, but it is not yet sufficient.

In general, the following conditions are required as a flame retardant for a polyurethane foam.

(1) Scoring (form numbering) should not occur

(2) There must be a persistence of flame retardancy of foam.

(3) Appropriate viscosity

(4) Good compatibility with foam components

(5) It should be difficult to hydrolyze

(6) Reduce smoke or poison gas

(7) Do not deteriorate the properties of the foam

(8) Excellent fogging resistance

(9) VOC, low molecular weight mono-type compound should be few

Among the above-mentioned various conditions, it is particularly required that the polyurethane foam does not generate scouring, has good flame retardancy, and also has low physical property degradation, excellent fogging resistance, and low VOC and low molecular weight single-molecular compound. do. In particular, in recent years, demands for a fogging resistance, a VOC, and a low-molecular-weight monomer compound have been increasing.

Conventionally, tris(2-chloroethyl)phosphate, tris(chloropropyl)phosphate, tris(dichloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, and the like have been used as flame retardants for polyurethane foams.

Organic phosphorus compounds such as tris (2-chloroethyl) phosphate and tris (dichloropropyl) phosphate initially exhibit flame retardant effects when formulated in polyurethane foams, but the flame retardant effect is remarkably deteriorated with changes over time. There is a problem that gingham is poor, and there are many VOCs and low molecular weight single-molecular compounds. This is considered to be because the molecular weight of these organophosphorus compounds is small and the flame retardant volatilizes.

Further, tris(2,3-dibromopropyl)phosphate is excellent in terms of flame retardancy and durability, but is inferior in heat resistance, and when added to a polyurethane foam, scouring occurs during foam production, which is not preferable. Can not do it.

Further, tris(2,3-dibromopropyl)phosphate was also used as a flame retardant for polyester fibers, but it is not currently used because of suspicion of carcinogenicity.

Recently, a compound having two phosphorus atoms in one molecule, 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate) (see Patent Document 1) and tetrakis(2-chloroethyl) Ethylene diphosphate (see Patent Document 2) is drawing attention as a flame retardant for polyurethane foams. However, these compounds are not sufficient in terms of flame retardancy and persistence, and it is necessary to use chlorine gas during production, which is problematic in terms of production.

So, in order to improve these, tris[bis(2-chloroethoxy)phosphinyl(dimethyl)methyl]phosphate, 2-chloroethyl bis[bis(2-chloroethoxy)phosphinyl(dimethyl)methyl]phosphate It has been studied (see Patent Documents 3 and 4).

However, these compounds contain phosphorus compound monomers such as tris (2-chloroethyl) phosphate by-product in the manufacturing process, and do not sufficiently respond to the demand for reduction of fogging resistance, VOC, and low molecular weight monomeric compounds, The development of such halogen-containing organophosphorus compounds and methods for their preparation has been desired.

US Patent No. 3122422 Specification Japanese Patent Publication S49-43272 Japanese Patent Publication S56-36512 Japanese Patent Application Publication H11-100391

The present invention exhibits excellent flame retardancy as a flame retardant for resins, especially as an additive type flame retardant when flame retarding polyurethane foams, and furthermore, has little change over time in durability, excellent fogging resistance, and a single-molecular compound of VOC and low molecular weight. An object of the present invention is to provide a flame retardant for a resin having a small amount of a polyphosphonate phosphate type organic phosphorus compound as a main component, a flame retardant resin composition containing the same, and a method for producing the organic phosphorus compound.

The present inventors have conducted extensive studies to solve the above problems, and as a result, a low molecular weight single-molecular compound, i.e., a polyphosphonate phosphate-type organic phosphorus compound having a reduced content of a phosphate ester monomer, is used for resins, especially polyurethane foams. An excellent flame retardant that satisfies most of the various conditions of the flame retardant, and a method for producing the organophosphorus compound, have been discovered and the present invention has been completed.

Thus, according to the present invention, in the flame retardant for a resin containing an organophosphorus compound of the formula (I),

When the organophosphorus compound was measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the following formula (I) is 0.1 to 3.0 area%, and n=0 in the following formula (I) Flame retardants for resins having an average condensation degree (N) of 1.5 to 3.5 calculated from the content of each compound of -10 are provided:

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or a haloalkyl group having 1 to 8 carbon atoms, Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10.

Moreover, according to this invention, the flame retardant resin composition containing the said flame retardant for resins and resin is provided.

In addition, according to the present invention,

As the step (1), the compound (c) of the compound (a) of the formula (a), the compound (b) of the formula (b), and the compound (c) of the formula (c) per 1 mol of the compound (a) ) In a ratio of 1.5 to 3.5 mol, and further reacting the compound (b) in a proportion of 1.3 to 2.0 mol with respect to 1 mol of the compound (c) at a temperature of -20 to 60 deg. The step of obtaining the compound (d),

Subsequently, as step (2), compound (d) obtained in step (1) is oxidized with an oxidizing agent, represented by the formula (I), and measured by GPC, n=0 in the formula (I) A step of obtaining an organophosphorus compound having an average condensation degree (N) of 1.5 to 3.5 calculated from the content of each compound of n = 0 to 10 in the formula (I), wherein the content of the compound is 0.1 to 3.0 area%. A method of preparing an organophosphorus compound comprising, is provided:

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ and n have the same meaning as defined in formula (I), R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, and X is It is a halogen atom.

According to the present invention, as a flame retardant for resins, in particular as an additive type flame retardant when flame retarding polyurethane foams, it exhibits excellent flame retardancy, furthermore, little change over time in durability, excellent fogging resistance, and a single-molecular weight type of VOC and low molecular weight It is possible to provide a flame retardant for a resin containing as a main component a polyphosphonate phosphate type organic phosphorus compound with few compounds, a flame retardant resin composition comprising the same, and a method for producing the organic phosphorus compound.

The flame retardant for resins of the present invention exhibits excellent flame retardant effect by adding to the resin, in particular, to the polyurethane foam component before foaming by a prescribed prescription, with very little volatility of the main component of the organophosphorus compound of formula (I). . The obtained polyurethane foam shows excellent flame retardancy and fogging resistance (low volatility) by a combustibility test method such as MVSS-302, as described later, and has very little volatile content.

The flame retardant for resins of the present invention exerts the above effect when the following conditions are satisfied:

ㆍWhen the organic phosphorus compound was measured by GPC, the content of the compound of n=1 in the formula (I) is 10 to 50 area%,

ㆍThe average condensation degree (N) in the formula (I) is 1.8 to 3.0.

In addition, the flame retardant resin composition of the present invention exhibits the above effects when the following conditions are satisfied:

ㆍResin, especially polyurethane resin, is a resin selected from polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, styrene resin and synthetic rubber. Urethane foam,

ㆍIt contains 1 to 40 parts by weight of the flame retardant for the resin with respect to 100 parts by weight of the resin.

In addition, the method for producing the organophosphorus compound of the present invention exhibits the above effect when the following conditions are satisfied:

ㆍWhen the organic phosphorus compound was measured by GPC, the content of the compound of n=1 in the formula (I) is 10 to 50 area%,

ㆍThe average condensation degree (N) in the formula (I) is 1.8 to 3.0.

1 is a view showing the flame retardancy of the flame retardant for a resin of the present invention.
It is a figure which shows the retention rate of personnel content of the resin flame retardant of this invention.

In the flame retardant for a resin of the present invention, in the resin flame retardant containing an organophosphorus compound of the formula (I),

When the organophosphorus compound was measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the following formula (I) is 0.1 to 3.0 area%, and n=0 in the hungry formula (I). It is characterized by an average degree of condensation (N) calculated from the content of each compound of -10 being 1.5 to 3.5:

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or a haloalkyl group having 1 to 8 carbon atoms, Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10.

In addition, in this invention, "A-B" showing a numerical range means A or more and B or less.

Hereinafter, [1] an organophosphorus compound of formula (I) contained in the flame retardant for resins of the present invention (hereinafter also referred to as "organic phosphorus compound (I)"), [2] preparation of an organophosphorus compound (I) The method and [3] will be described in the order of the flame-retardant resin composition of the present invention.

[1] organophosphorus compounds (I)

The organophosphorus compound (I) contained in the flame retardant for resins of the present invention is represented by the formula (I).

The substituents R ₁ , R ₂ , R ₃ and R ₄ in the formula (I) are each independently an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group, and having 1 to 1 carbon atoms. The haloalkyl group of 4 is more preferable.

Examples of the halogen atom of the haloalkyl group include fluorine, chlorine, bromine and iodine, chlorine and bromine are preferred, and chlorine is particularly preferred.

Specific examples of the substituent include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, n-octyl, isooctyl, 2-ethylhexyl: chloromethyl, chloroethyl, chloropropyl, and chloroisopropyl , Dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl, bromomethyl, bromoethyl, bromopropyl, bromoisopropyl, dibromopropyl, dibromoisopropyl, bromobutyl, And haloalkyl groups such as dibromobutyl, dibromoisobutyl, bromochloropropyl, bromochloroisopropyl, bromochlorobutyl, and bromochloroisobutyl.

Among these, chloromethyl, chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl, bromomethyl, bromoethyl, bromopropyl, bromoisopropyl, Carbon number such as dibromopropyl, dibromoisopropyl, bromobutyl, dibromobutyl, dibromoisobutyl, bromochloropropyl, bromochloroisopropyl, bromochlorobutyl, bromochloroisobutyl The haloalkyl group of 1 to 4 is more preferable, and chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl, and dichloroisopropyl are particularly preferable.

The substituents Z ₁ and Z ₂ in the formula (I) are each independently a hydrogen atom, a methyl group or an ethyl group.

The number of repeating units n in the formula (I) is 0 to 10, and the compound as a component constituting the organophosphorus compound (I) is a mixture of compounds in which n is 0 to 10, but the values of n are different and the degree of condensation is different. , Basically, the properties as the flame retardant for resins are almost the same.

In this way, n in the formula (I) can take from 0 to 10, but considering the workability and the effect obtained as a flame retardant for a resin and a flame retardant resin composition, the viscosity needs to be appropriate.

In addition, in order to provide a flame retardant for resins having excellent fogging resistance and few phosphate ester monomers, it is preferable that n of the compound serving as the main component of the organophosphorus compound (I) is any one of 1 to 5, and any one of 1 to 3 It is particularly preferred.

The specific number of repeating units n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, 1, 2, 3, 4 and 5 are preferred, and 1, 2 and 3 are particularly preferred. Do.

Here, the main component means the component having the most content among the components constituting the organophosphorus compound (I).

Therefore, the organic phosphorus compound (I) contained in the flame retardant for resins of the present invention has a content of a compound of n=0 in the formula (I) when measured by gel permeation chromatography (GPC) described later. It is 0.1 to 3.0 area%, and the average degree of condensation (N) calculated from the content of each compound of n=0 to 10 in formula (I) is 1.5 to 3.5.

The specific content of n=0 compound (area %) is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 , 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3.0.

It is most preferable that the organophosphorus compound (I) does not contain a compound of n=0 in the formula (I), that is, a monomeric phosphoric acid ester, but since it is by-product in the manufacturing process, n= in the formula (I) The compound of 0 may be contained as long as it is 0.1 to 3.0 area% in GPC measurement.

Moreover, from the above reason, it is preferable that the content of the compound of n=1 in the formula (I) is 10 to 50 area% in GPC measurement. As for the upper limit, 45 area% is more preferable, and 40 area% is more preferable. The lower limit is more preferably 15 area%, more preferably 20 area%.

The content (area %) of a specific n=1 compound is, for example, 10, 15, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 , 35, 36, 37, 38, 39, 40, 45 and 50 etc.

In view of the above, the average condensation degree (N) of the organophosphorus compound (I) is 1.5 to 3.5. The upper limit is more preferably 3.0. Moreover, as for the lower limit, 1.8 is more preferable, and 2.0 is more preferable.

Specific average condensation degree (N) is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 and 3.5.

The average condensation degree (N) can be calculated by the following equation using the GPC area fraction (A _n ) of each component of n=0 to 10 in GPC measurement.

N=Σ(nㆍA _n )/Σ(A _n )

The content of each compound (component) of n=0 to 10 of the organophosphorus compound (I) by GPC measurement can be analyzed (measured) as follows, for example.

Specifically, 10 mL of tetrahydrofuran (THF) is added to a sample of 0.09 g by a hole pipette, the sample solution is analyzed by the following instruments and analysis conditions, and the area percentage of the RI detector is the content of each compound (composition). Is done.

(device)

GPC analyzer (TOSOH CORPORATION., model: HLC-8220 or equivalent)

Data analysis device (TOSOH CORPORATION., format: SC-8010 or equivalent)

(column)

Guard column

(TOSOH CORPORATION., Type: TSKguardcolumnSuperHZ-L

1 x 4.6mm I.D.×2.0cm)

Sample column

(TOSOH CORPORATION., Type: TSKGEL SuperHZ1000

6.0mmI.D.×15cm) 3 pcs.

(TOSOH CORPORATION., Type: TSKGEL SuperHZ2000

1x 6.0mmI.D.×15cm)

(Analysis conditions)

INLET temperature 40℃

Column temperature 40℃

RI temperature 35℃

Solvent flow rate 0.25 ml/min

Detector RI (Refractive Index)

Sample solution injection volume 10µl (Loop tube)

(Data processing conditions)

START TIME (minutes) 25.00

STOP TIME (minutes) 50.00

Examples of the polyphosphonate phosphate type organic phosphorus compound (I) of the present invention include compounds having a combination of the above substituents and the number of repeating units, and may be a mixture of two or more different substituents.

Among these, as a compound of n=1,

1-[bis(2-chloroethoxy)phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate, and

1-[bis(2-chloroethoxy)phosphinyl]ethylbis(2-chloroethyl)phosphate, and

The condensate represented by n=2 or more of these is particularly preferable.

The flame retardant for resins containing the polyphosphonate phosphate type organic phosphorus compound of the formula (I) of the present invention can be used as a flame retardant for various resins.

Preferred resins to be added include, for example, polyurethane resins, acrylic resins, phenol resins, epoxy resins, vinyl chloride resins, polyamide resins, polyester resins, unsaturated polyester resins, styrene resins and synthetic rubbers. have. Among these, polyurethane resins and acrylic resins are preferred, polyurethane resins are more preferred, and foams of polyurethane resins, that is, polyurethane foams are particularly preferred.

The polyurethane foam may be soft, semi-rigid, or hard, and the flame retardant of the present invention can be suitably used as an additive flame retardant.

Since the polyurethane foam has a breathable continuous cell, in a conventional flame retardant for resin, it is volatilized and scattered, flame retardancy persists, or its function may be lost, or fogging resistance may decrease. Moreover, there was also a problem that there were many phosphoric acid ester monomers. In the flame retardant for resins of the present invention, there are few volatile components, it continuously exhibits flame retardancy, improves fogging resistance, and can reduce the phosphate ester monomer.

[2] Method for producing organophosphorus compound (I)

The organophosphorus compound (I) of the present invention can be produced, for example, by a known two-step reaction under the conditions described below.

That is, compound (a), (b) and (c) are reacted by step (1) to obtain compound (d), and then compound (d) obtained in step (1) is obtained by step (2). It can be obtained by oxidizing with an oxidizing agent.

Steps (1) and (2) can theoretically be represented by the following reaction formulas (1) and (2), respectively (where OA represents an oxidizing agent).

Hereinafter, each process is demonstrated.

Process (1)

In the step (1), compounds (a), (b) and (c) are compounded with a ratio of 1.5 to 3.5 moles of compound (c) relative to 1 mole of compound (a), and further 1 mole of compound (c) With respect to, the compound (b) is reacted at a temperature of -20 to 60°C in a ratio of 1.3 to 2.0 mol to obtain the compound (d). That is, q=1.5-3.5, and p/q=1.3-2.0. By reaction of compounds (a), (b) and (c), RX (R is the same meaning as R ₁ , R ₂ , R ₃ , R ₄ and R ₅ and X is a halogen atom) is eliminated. .

In the above formula, "+OA" means adding an oxidizing agent.

Here, the reason why the value of the coefficient q is set to q = 1.5 to 3.5 will be explained.

Since the average condensation degree (N) of the organophosphorus compound (I) of the present invention is theoretically a condensation degree corresponding to the coefficient q in Reaction Formula (1), the average condensation degree (N) is defined in the present invention. In order to make it into a range, the ratios of the compounds (a), (b) and (c) can be used in corresponding molar multiples.

In step (1), the coefficient q of compound (c) must exceed 1.

This is because, when the coefficient q is less than 1, unreacted compound (a) necessarily exists, which is a cause of the production of the short-term phosphate ester represented by n=0 in compound (d) and formula (I).

In addition, when the coefficient q is 1, the theoretical reaction formula does not produce a monomeric phosphate ester represented by n=0 in the formula (I), but the reaction rate cannot be 100%, so the compound (d) and the formula This is because, in order to reduce the content of the monomeric phosphate ester represented by n=0 in (I), the coefficient q must exceed 1.

In addition, the reason why the ratio with q is p/q=1.3-2.0 will be described for the value of the coefficient p.

In the reaction of step (1), compound (b) binds between compound (a) and compound (c) and exhibits the same behavior as a condensing agent. Therefore, in the theoretical reaction formula, compound (b) will generate compound (d) in equimolarity with compound (c), but in reality, the reaction rate cannot be 100%. Therefore, it is necessary to add the compound (b) in an excessive amount.

As described above, the compounds (a), (b) and (c) are condensed reliably, and the average degree of condensation (N) is set to 1.5 to 3.5 without remaining unreacted compounds (a) and (c). In order to do so, it is necessary to use compound (c) in a ratio of 1.5 to 3.5 moles per 1 mole of compound (a). That is, q=1.5-3.5. The upper limit is preferably 3.0, and the lower limit is preferably 1.7. Moreover, at the same time, it is also necessary to use compound (b) at a ratio of 1.3 to 2.0 moles per 1 mole of compound (c). That is, p/q=1.3-2.0. The upper limit is preferably 1.7, and the lower limit is preferably 1.4.

The values of the specific coefficients q are, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3.0.

In addition, the ratio p/q between the value of the specific coefficient p and q is, for example, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2.0.

The reaction temperature in step (1) is -20 to 60°C.

If the reaction temperature is lower than -20°C, the reaction may be slow and may not proceed sufficiently. On the other hand, when the reaction temperature is higher than 60°C, the reaction proceeds rapidly, and control may be difficult. The lower limit of the reaction temperature is preferably -10°C, and more preferably 0°C. The upper limit is preferably 50°C, more preferably 40°C.

Specific reaction temperatures (°C) are, for example, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 and 60, etc. .

Here, it is preferable that the substituents R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are all the same.

When all of these substituents are the same haloalkyl group, by reacting by controlling the molar ratio of the corresponding alkylene oxide and phosphorus trihalide to react, the phosphite compound (a) and the phosphoro compound (c) in step (1) are reacted. Halidite can be prepared simultaneously.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, and tetramethylene oxide. Among these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is particularly preferable.

The amount of compound (b) required can be calculated by measuring the active halogen atom (X) in the reaction solution at this time and calculating the concentration of the X atom in compound (c).

For example, when R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are chloroethyl groups, and the active halogen atom is chlorine, the concentration of the active halogen atom is preferably 9 to 11% by weight, and 9 to 10% by weight Is more preferred.

Specific active halogen atom concentration (% by weight) is, for example, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7 , 10.8, 10.9 and 11.0.

Next, the raw material compound in step (1) will be described.

Compound (a) is represented by the following formula.

In the above formula, R ₁ and R ₂ have the same meaning as defined in formula (I), and R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group.

Examples of the alkyl group and haloalkyl group having 1 to 8 carbon atoms in R ₅ include those exemplified in formula (I) as R1 and R2.

Compound (a) is trialkylphosphite or tris(haloalkyl)phosphite, for example known methods such as those described in U.S. Pat.No. 3,82,3272, specifically phosphorus trichloride and alkylalcohols or alkylene oxides. It can be prepared by reaction with.

Specific examples of the compound (a) are trimethylphosphite, triethylphosphite, methyldiethylphosphite, dimethylethylphosphite, tripropylphosphite, methylethylpropylphosphite, triisopropylphosphite, tributylphosphite, tri Isobutylphosphite, trihexylphosphite, tricyclohexylphosphite, tri(n-octyl)phosphite, tri(isooctyl)phosphite, tri(2-ethylhexyl)phosphite, tris(chloromethyl)phosphite , Tris(chloroethyl)phosphite, chloromethyldi(chloroethyl)phosphite, di(chloromethyl)chloroethylphosphite, tris(chloropropyl)phosphite, tris(dichloropropyl)phosphite, chloroethyldi(chloro Propyl)phosphite, di(chloroethyl)chloropropylphosphite, chloromethylchloroethylchloropropylphosphite, tris(chloroisopropyl)phosphite, chloroethyldi(chloroisopropyl)phosphite, di(chloroethyl)chloro Isopropylphosphite, chloromethylchloroethylchloroisopropylphosphite, tris(dichloroisopropyl)phosphite, tris(bromomethyl)phosphite, tris(bromoethyl)phosphite, tris(bromopropyl)phosphite , Tris(dibromopropyl)phosphite, tris(bromoisopropyl)phosphite, tris(dibromoisopropyl)phosphite, tris(bromochloropropyl)phosphite, tris(bromochloroisopropyl) And phosphites. Among these, tris(chloroethyl)phosphite, tris(chloropropyl)phosphite, tris(dichloropropyl)phosphite, tris(chloroisopropyl)phosphite, tris(dichloroisopropyl) Phosphite is particularly preferred.

Compound (b) is represented by the following formula.

In the above formula, Z ₁ and Z ₂ have the same meaning as defined in formula (I).

Specific examples of the compound (b) include formaldehyde, acetaldehyde, propionaldehyde, acetone, methyl ethyl ketone, and diethyl ketone. Among these, acetaldehyde, acetone, and methyl ethyl ketone are preferable, and acetaldehyde and acetone This is more preferred, and acetone is particularly preferred.

Compound (c) is represented by the following formula.

In the above formula, R ₃ and R ₄ have the same meaning as defined in formula (I), and X is a halogen atom.

X may include fluorine, chlorine, bromine and iodine as halogen atoms, chlorine and bromine are preferred, and chlorine is particularly preferred.

Compound (c) is a dialkyl phosphorohalide or di(haloalkyl)phosphohalodate, and the reaction is stopped with a diester by a known method, for example, as described in U.S. Pat. Specifically, it can be produced by stopping reaction of phosphorus trihalide such as phosphorus trichloride with alkyl alcohol or alkylene oxide with a diester.

Specific examples of the compound (c) include dimethyl phosphorochloridite, diethyl phosphorochloridite, methyl ethyl phosphorochloridite, dipropyl phosphorochloridite, methylpropylphosphorochloridite, and ethylpropylphosphoro Chloridite, diisopropylphosphorochloridite, ethylisopropylphosphorochloridite, dibutylphosphorochloridite, diisobutylphosphorochloridite, dihexylphosphorochloridite, dicyclohexyl Phosphorochloridite, di(n-octyl)phosphorochloridite, di(isooctyl)phosphorochloridite, di(2-ethylhexyl)phosphorochloridite, di(chloromethyl)phospholoclo Lidite, di (chloroethyl) phosphorochloridite, chloromethyl chloroethyl phosphorochloridite, di (chloropropyl) phosphorochloridite, chloroethyl chloropropyl phosphorochloridite, di (dichloropropyl) Phosphorochloridite, di (chloroisopropyl) phosphorochloridite, chloroethyl chloroisopropyl phosphorochloridite, di (dichloroisopropyl) phosphorochloridite, di (bromomethyl) phosphoroclo Lidite, di (bromoethyl) phosphorochloridite, di (bromopropyl) phosphorochloridite, di (dibromopropyl) phosphorochloridite, di (bromoisopropyl) phosphoroclo Lidite, di (dibromoisopropyl) phosphorochloridite, di (bromochloropropyl) phosphorochloridite, di (bromochloroisopropyl) phosphorochloridite, etc. are mentioned, These Among them, di (chloroethyl) phosphorochloridite, di (chloropropyl) phosphorochloridite, di (dichloropropyl) phosphorochloridite, di (chloroisopropyl) phosphorochloridite, di (dichloro) Isopropyl) phosphorochloridite is particularly preferred.

Process (2)

In step (2), the compound (d) obtained in step (1) is oxidized with an oxidizing agent to obtain the organophosphorus compound (I) of the present invention. That is, in step (2), the phosphite portion of compound (d) is oxidized.

Specific examples of the oxidizing agent include peracetic acid and hydrogen peroxide, and hydrogen peroxide is particularly preferred. As the hydrogen peroxide, an aqueous solution may be used, and 35 (weight/volume)% hydrogen peroxide water frequently used for industrial use is particularly preferable.

In the step (2), an aqueous sodium hydroxide solution is appropriately added to the reaction solution, if necessary, and hydrogen peroxide can be added dropwise while maintaining the reaction solution at pH 9.5 to 10.5. As an aqueous sodium hydroxide solution, a 30 (weight/volume)% aqueous solution frequently used for industrial use is preferable.

Specific pH is, for example, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4 and 10.5.

The reaction temperature in step (2) is preferably 5 to 50°C, the upper limit is preferably 40°C, and the lower limit is preferably 10°C.

Specific reaction temperatures (°C) are, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50.

As described above, the method for producing the organophosphorus compound (I) of the present invention has been described, but it is possible to produce many compounds depending on the choice of the types of phosphites, phosphorohalides, aldehydes and ketones which are the main raw materials for the reaction. It goes without saying that they are within the scope of the present invention.

In addition, the method for producing the organophosphorus compound (I) of the present invention has the advantage that the phosphorus content, the halogen content, the molecular weight, etc. can be adjusted and various organophosphorus compounds (I) can be prepared according to the purpose.

In actual production, a desired compound is obtained by selecting a desired compound from these compounds, and may be a mixture of two or more compounds, or a mixture of different condensation degrees, but in order to achieve excellent fogging resistance, in the formula (I) It is necessary to make the content of the monomeric phosphate ester represented by n=0 of as small as possible.

[3] flame retardant resin composition

The flame retardant resin composition of the present invention is characterized by containing the flame retardant for the resin of the present invention and a resin.

Examples of the resin include resins exemplified as an object of addition of a resin flame retardant.

It is preferable that the flame retardant resin composition of the present invention contains 1 to 40 parts by weight of a flame retardant for resin relative to 100 parts by weight of the resin. The amount of the flame retardant for the resin to be added may be appropriately set depending on the type of the resin or the desired degree of flame retarding.

Addition amount (part by weight) of the flame retardant for resin to 100 parts by weight of the specific resin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35 and 40.

The flame retardant resin composition using the organophosphorus compound of the present invention may contain known resin additives, that is, other flame retardants or additives other than flame retardants, within a range that does not adversely affect the properties of the resin.

Examples of other flame retardants include non-halogen phosphate ester flame retardants such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcinol-tetraphenyl bisphosphate, and bisphenol A-tetraphenyl bis phosphate; 2,2bis(chloromethyl)-1,3-propanebis(chloroethyl)diphosphate, tetrakis(2-chloroethyl)ethylenediphosphate, (poly)alkylene glycol-based halogen-containing polyphosphate, tris(tribro) Parent) halogen-containing phosphate ester flame retardants such as neopentyl phosphate; Bromine flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, 1,2-bis(pentabromophenyl)ethane; Inorganic flame retardants such as antimony trioxide and magnesium hydroxide; And nitrogen-based flame retardants such as ammonium polyphosphate and melamine phosphate.

As additives other than flame retardants, antioxidants, fillers, lubricants, modifiers, fragrances, antibacterial agents, pigments, dyes, heat resistant agents, weathering agents, antistatic agents, UV absorbers, stabilizers, strengthening agents, drip inhibitors, antiblocking agents, wood powder, starch, etc. Can be heard.

The flame retardant for resins, which is an organic phosphorus compound of the present invention, can be particularly suitably used for polyurethane foams, and the flame retardant resin composition containing the flame retardant for resins and polyurethane foams of the present invention, that is, flame retardant polyurethane foams, is an existing organic phosphorus compound Compared to the polyurethane foam flame-retardant by the flame retardant of the system, it has excellent flame retardancy and durability, and further has excellent anti-fogging performance.

The manufacturing method of the polyurethane foam is already known, and a flame-retardant polyurethane foam to which a flame retardant is added can also be produced by a known method.

For example, 1 to 30 parts by weight, preferably 3 to 20 parts by weight of the flame retardant for the resin of the formula (I) of the present invention is mixed with respect to 100 parts by weight of the polyol containing polyester polyol, polyether polyol and the like. A flame retardant polyurethane foam is obtained by adding a foam stabilizer, a catalyst, a blowing agent, and the like to the obtained mixture, stirring, and then adding and reacting an organic polyisocyanate.

The amount of the flame retardant for resin (parts by weight) added to 100 parts by weight of the specific polyol is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30.

Examples of the organic polyisocyanate include tolylene diisocyanate, phenylenediisocyanate, xylene diisocyanate, biphenyl disisocyanate, naphthalene disisocyanate, diphenylmethane diisocyanate, cyclopentane diisocyanate, cyclohexane diisocyanate, isophorone di Isocyanate, norbornane diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate , 1,3-butylene diisocyanate, and the like.

Example

The present invention will be described more specifically by the following examples and comparative examples, but the scope of the present invention is not limited by these.

[ Example One]

(Reaction process: Process (1))

A 1000 ml flask equipped with a stirring bar, thermometer, blowing tube, and condenser was charged with 275 g (2.0 mol) of phosphorus trichloride, 0.55 g of triethylamine and 0.65 g of ethylene chlorohydrin. Subsequently, the obtained mixture was heated to 40-50°C under stirring, and 208 g (4.72 mol) of gaseous ethylene oxide was blown over 4 hours by passing a flow meter and a blowing tube from a cylinder. Thereafter, the mixture was heated to 50 to 60°C and maintained (aged) for 1 hour, followed by tris(2-chloroethyl)phosphite as compound (a) and di(2-chloroethyl)phosphorochloridet as compound (c). Mixtures (0.70 mol and 1.30 mol, respectively) were obtained. The active chlorine concentration of the reaction mixture was 9.6%.

The obtained reaction mixture was kept at 0 to 10°C, and 113 g (1.95 mol) of acetone as 1.5 mol of compound (b) relative to 1 mol of di(2-chloroethyl)phosphochlorochloride as compound (c) was maintained. , Added over 2 hours through a dropping funnel. After reacting at the same temperature for 12 hours, the reaction temperature was gradually raised and reacted at 30-40°C for 24 hours. The acid value of the reaction mixture was 2.2.

(Reaction process: Process (2))

Thereafter, the reaction mixture containing the obtained compound (d) was maintained at 5 to 10°C, and 6 g of a 30% aqueous sodium hydroxide solution was added through a dropping funnel. The pH of the reaction mixture was 10.5.

Then, the obtained reaction mixture was maintained at 10 to 20°C, and 71 g (0.73 mol) of a 35% aqueous hydrogen peroxide solution as an oxidizing agent was added over 4 hours. While the aqueous hydrogen peroxide solution was added, the pH was adjusted while adding a 30% aqueous sodium hydroxide solution appropriately so that the pH of the reaction mixture became 9.5 to 10.5. The total amount of the 30% aqueous sodium hydroxide solution was 25 g. After the completion of the addition of the aqueous hydrogen peroxide solution, the reaction was continued at 30 to 40°C for 2 hours.

(Post-treatment process)

To the obtained reaction mixture, 10 g of a 30% aqueous sodium hydroxide solution was added, heated to 40 to 50°C, and stirred for 1 hour. Subsequently, the obtained reaction mixture was standing in an aliquot, and separated into an aqueous phase and an organic phase. The obtained organic phase was washed twice with 200 ml of hot water at 60 to 70° C., and then a low boiling point portion was removed at 90 to 100° C. under reduced pressure of 1 to 3 kPa. The obtained product is referred to as flame retardant A.

As a result of analyzing the flame retardant A, the main component is 1-[bis(2-chloroethoxy), wherein R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 0.9 area%, the compound of n=1 was 37.2 area%, and the average degree of condensation (N) was 2.12.

The phosphorus content (P) was 13.8% by weight, the chlorine content (Cl) was 26.1% by weight, the viscosity was 4320 mPa·s (25°C), and the acid value was 0.03 KOHmg/g.

[ Example 2]

Tris(2-chloroethyl)phosphite as compound (a) and di(2) as compound (c) were prepared in the same manner as in Example 1, except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g (4.70 mol). -Chloroethyl) A mixture with phosphorochloridite (0.65 mol and 1.35 mol, respectively) was obtained. The active chlorine concentration of the reaction mixture was 10.0%.

Further, the obtained reaction mixture was maintained at 40°C instead of 0 to 10°C, and 116 g of acetone as 1.5 mol of compound (b) to 1 mol of di(2-chloroethyl)phosphorochloride as compound (c) (2.00 mol) was added over 6 hours instead of 2 hours through a dropping funnel, reacted at the same temperature for 12 hours, and changed 71 g (0.73 mol) of 35% hydrogen peroxide aqueous solution as an oxidizing agent to 65 g (0.67 mol). The flame retardant B was obtained like Example 1 except having done.

As a result of analyzing the flame retardant B, the main component is 1-[bis(2-chloroethoxy) in which R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethyl bis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 0.5 area%, the compound of n=1 was 29.2 area%, and the average degree of condensation (N) was 2.41.

The phosphorus content (P) was 13.9% by weight, the chlorine content (Cl) was 24.8% by weight, the viscosity was 6200 mPa·s (25°C), and the acid value was 0.05 KOHmg/g.

[ Example 3]

In the same manner as in Example 1, a mixture of tris (2-chloroethyl) phosphite and di (2-chloroethyl) phosphorochloridite was obtained.

Further, the obtained reaction mixture was maintained at 40°C instead of 0 to 10°C, and 128 g of acetone as 1.7 mol of compound (b) relative to 1 mol of di(2-chloroethyl)phosphochlorochloride as compound (c) (2.20 mol) was added over 6 hours instead of 2 hours through a dropping funnel and reacted at the same temperature for 12 hours. 71 g (0.73 mol) of 35% aqueous hydrogen peroxide solution as an oxidizing agent was changed to 65 g (0.67 mol). Flame retardant C was obtained in the same manner as in Example 1 except for the above.

As a result of analyzing the flame retardant C, the main component is 1-[bis(2-chloroethoxy), wherein R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethyl bis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 1.3 area%, the compound of n=1 was 34.7 area%, and the average degree of condensation (N) was 2.16.

The phosphorus content (P) was 13.7% by weight, the chlorine content (Cl) was 25.1% by weight, the viscosity was 2200 mPa·s (25°C), and the acid value was 0.02 KOHmg/g.

[ Example 4]

Tris(2-chloroethyl)phosphite as compound (a) and di(2) as compound (c) were prepared in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 198 g (4.50 mol). -Chloroethyl) A mixture of phosphorochloridite (0.59 mol and 1.40 mol, respectively) was obtained. The active chlorine concentration of the reaction mixture was 10.5%.

Further, the obtained reaction mixture was maintained at 40°C rather than 0 to 10°C, and 123 g of acetone as 1.5 mol of compound (b) to 1 mol of di(2-chloroethyl)phosphorochloride as compound (c) (2.12 mol) was added over 6 hours instead of 2 hours through a dropping funnel, reacted at the same temperature for 12 hours, and changed 71 g (0.73 mol) of 35% hydrogen peroxide aqueous solution as an oxidizing agent to 60 g (0.62 mol). The flame retardant D was obtained like Example 1 except having done.

As a result of analyzing the flame retardant D, the main component is 1-[bis(2-chloroethoxy), wherein R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethylbis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 0.5 area%, the compound of n=1 was 22.9 area%, and the average degree of condensation (N) was 2.70.

The phosphorus (P) was 14.2% by weight, the chlorine (Cl) was 24.5% by weight, the viscosity was 7700 mPas (25°C), and the acid value was 0.05 KOHmg/g.

[ Example 5]

Tris(2-chloroethyl)phosphite as compound (a) and di(2) as compound (c) were prepared in the same manner as in Example 1, except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g (4.70 mol). -Chloroethyl) A mixture of phosphorochloridite (0.73 mol and 1.27 mol, respectively) was obtained. The reaction mixture had an active chlorine concentration of 9.4%.

Further, the obtained reaction mixture was maintained at 40°C instead of 0 to 10°C, and 97 g of acetone as 1.3 mol of compound (b) relative to 1 mol of di(2-chloroethyl)phosphochlorochloride as compound (c) Flame retardant E was obtained in the same manner as in Example 1 except that (1.67 mol) was added through the dropping funnel over 6 hours instead of 2 hours and reacted at the same temperature for 12 hours.

As a result of analyzing the flame retardant E, the main component is 1-[bis(2-chloroe) in which R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. It was found that it was methoxy)phosphinyl]-1-methylethyl bis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 2.4 area%, the compound of n=1 was 30.4 area%, and the average degree of condensation (N) was 2.22.

The phosphorus content (P) was 13.8% by weight, the chlorine content (Cl) was 25.1% by weight, the viscosity was 3850 mPa·s (25°C), and the acid value was 0.06 KOHmg/g.

[ Comparative example One]

Tris(2-chloroethyl)phosphite as compound (a) and di(2) as compound (c) were prepared in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 222 g (5.05 mol). -Chloroethyl) A mixture of phosphorochloridite (1.03 mol and 0.95 mol, respectively) was obtained. The active chlorine concentration of the reaction mixture was 6.9%.

Further, the obtained reaction mixture was maintained at 40°C instead of 0 to 10°C, and 64 g of acetone as 1.1 mol of compound (b) to 1 mol of di(2-chloroethyl)phosphorochloride as compound (c) (1.10 mol) was added over 6 hours instead of 2 hours through a dropping funnel and reacted at the same temperature for 12 hours, and 71 g (0.73 mol) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was changed to 98 g (1.01 mol) The flame retardant F was obtained like Example 1 except having done.

As a result of analyzing the flame retardant F, the main component is 1-[bis(2-chloroethoxy), wherein R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethyl bis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 14.8 area%, the compound of n=1 was 59.3 area%, and the average degree of condensation (N) was 1.19.

The phosphorus content (P) was 13.0% by weight, the chlorine content (Cl) was 28.9% by weight, the viscosity was 520 mPa·s (25°C), and the acid value was 0.03 KOHmg/g.

[ Comparative example 2]

Tris(2-chloroethyl)phosphite as compound (a) and di(2) as compound (c) were prepared in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 215 g (4.90 mol). A mixture of -chloroethyl)phosphorochloridite (0.90 mol and 1.10 mol, respectively) was obtained. The active chlorine concentration of the reaction mixture was 8.0%.

Further, the obtained reaction mixture was maintained at 40°C instead of 0 to 10°C, and 77 g of acetone as 1.2 mol of compound (b) relative to 1 mol of di(2-chloroethyl)phosphorochloride as compound (c) (1.33 mol) was added over 6 hours instead of 2 hours through a dropping funnel, and reacted at the same temperature for 12 hours, and 87 g (0.89 mol) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was changed to 65 g (0.67 mol). The flame retardant G was obtained like Example 1 except having done.

As a result of analyzing the flame retardant G, the main component is 1-[bis(2-chloroethoxy), wherein R ₁ , R ₂ , R ₃ and R ₄ of the formula (I) are 2-chloroethyl, Z ₁ and Z ₂ are methyl. )Phosphinyl]-1-methylethyl bis(2-chloroethyl)phosphate.

As a result of GPC measurement, the compound of n=0 was 9.0 area%, the compound of n=1 was 54.8 area%, and the average degree of condensation (N) was 1.43.

The phosphorus content (P) was 13.4% by weight, the chlorine content (Cl) was 28.0% by weight, the viscosity was 850 mPa·s (25°C), and the acid value was 0.04 KOHmg/g.

Table 1 shows the results obtained.

Table 1 shows a commercially available tris(2-chloroethyl)phosphate (Supresta, product name: FyrolCEF) as a known flame retardant (flame retardant H) as a comparative reference example.

In this compound, n of formula (I) is 0, R ₁ , R ₂ and R ₃ are 2-chloroethyl, phosphorus (P) is 10.8% by weight, chlorine (Cl) is 36.6% by weight, viscosity is 45mPa· s (20°C).

From the results of Table 1, in the reaction of step (1), di(2-chloroethyl)phosphorochloride as compound (c) to 1 mol of tris(2-chloroethyl)phosphite as compound (a) Is 1.74 to 2.37 mol, and at the same time, acetone as compound (b) is used in a proportion of 1.3 to 1.7 mol with respect to 1 mol of di(2-chloroethyl)phosphochloridite as compound (c). In Examples 1 to 5, the content of the compound of n=0 in the formula (I) (monomer phosphoric acid ester) is 0.5 to 2.4 area%, and the average condensation degree (N) is 2.12 to 2.70. Was obtained.

On the other hand, the ratio of di(2-chloroethyl)phosphorochloridite as compound (c) to 0.92 and 1.22 moles relative to 1 mole of tris(2-chloroethyl)phosphite as compound (a), and further simultaneously In Comparative Examples 1 and 2 using acetone as the compound (b) at a ratio of 1.1 mol and 1.2 mol with respect to 1 mol of the di(2-chloroethyl)phosphorochloridite as the compound (c), in the formula (I), respectively An organic phosphorus compound having a content of n=0 of the compound (monomer phosphoric acid ester) of 14.8 area% and 9.0 area% was obtained. For this reason, the average condensation degree (N) of the organophosphorus compounds of Comparative Examples 1 and 2 was 1.19 and 1.43, respectively, lower than those of Examples 1 to 5.

Comparative Example 1 had a higher ratio of tris(2-chloroethyl)phosphite as compound (a) to di(2-chloroethyl)phosphochlorochloride as compound (c) than Comparative Example 2, It is thought that the content of the n=0 monomeric phosphoric acid ester increased.

[ Example 6]

Using the flame retardant A obtained in Example 1, a polyurethane foam (foam) was prepared by the following prescription and manufacturing method, and the flame retardancy, fogging resistance, flame retardancy, and retention of personnel content were evaluated.

(Prescription)

Polyol (Mitsui Chemicals Inc., trade name: actcol T-3000) 100 parts

Silicone oil (Dow Corning Toray Co., Ltd., trade name: SZ-584) 1.0 copies

Amine-based catalyst

(Air Products and Chemicals, Inc., product name: DABCO 33LV) 0.2 copies

(Air Products and Chemicals, Inc., product name: DABCO BL-11) 0.05 copies

Tin-based catalyst

(Air Products and Chemicals, Inc., product name: DABCO T-9) 0.35 copies

Blowing agent (water) 4.3 parts

(Methylene chloride) 8.0 parts

Flame retardant (flame retardant A) required part

Isocyanate (Tolylene diisocyanate: TDI)

(Mitsui Chemicals Inc., trade name: Cosmonate T-80 (80/20)) 58.2 copies

The above "parts" means parts by weight.

The added number of flame retardants was changed to 8, 10, 12 and 14 parts.

(Manufacturing method)

Polyol, silicone oil, catalyst, foaming agent and flame retardant are blended with the above-mentioned formula, and the mixture is uniformly mixed by stirring for 1 minute at 3000 rpm using a stirrer, and further tolylene diisocyanate is added, and the rotational speed is 3000 rpm. The mixture was stirred for 5 to 7 seconds, and immediately the contents were poured into a carton (200 mm in height) in a square (about 200 mm in height) bottom.

Foaming occurred immediately and the maximum volume was reached after a few minutes. The obtained foam was cured by standing in a furnace at 120°C for 30 minutes. The foam obtained was a white soft communication bubble cell structure.

[ Example 7]

A foam was prepared in the same manner as in Example 6, except that the flame retardant B obtained in Example 2 was used instead of the flame retardant A, and the flame retardancy, fogging resistance, flame retardancy, and retention of personnel content were evaluated.

[ Comparative example 3]

A foam was produced in the same manner as in Example 6, except that the flame retardant F obtained in Comparative Example 1 was used instead of the flame retardant A, and the flame retardancy, fogging resistance, flame retardancy, and retention of personnel content were evaluated.

[ Comparative example 4]

A foam was produced in the same manner as in Example 6, except that the flame retardant H of the comparative reference example was used instead of the flame retardant A, and the flame retardancy and fogging resistance were evaluated. Regarding flame retardance persistence and retention rate of personnel content, evaluation of fogging resistance was poor, so it could not withstand the test conditions and could not be tested.

(Flame retardancy evaluation)

A sample was cut from the obtained foam, and a combustion test was conducted under the following conditions.

Test method: FMVSS-302 method (Test method of safety standards for automobile interior products)

Horizontal combustion test of polyurethane foam

Test conditions: The ventilation was also adjusted to be 200 ml/cm 2 /sec.

(The ventilation degree was measured according to the JIS K6400-7 B method.)

Sample: 2 types of thickness 5mm and 13mm

The density was adjusted to be about 20 to 25 kg/m 3.

Acceptance criteria: A combustion distance of 38 mm or less was set as a pass.

Table 2 shows the obtained results.

(Evaluation of fogging resistance)

A sample was cut from the obtained foam, and a fogging test was conducted under the following conditions.

Test conditions: Wind screen fogging tester (Suga Test Instruments Co., Ltd.) was used, and a sample of polyurethane foam (diameter 80 mm, thickness 10 mm) was installed under the container, and the sample was heated at 100° C. for 16 hours. , The amount of the fly products from the sample adhering to the glass plate on the container top was measured by the amount of glass attached (mg).

Sample: 1 type of 8 parts added to the flame retardant

Table 3 shows the obtained results.

From the results of Table 2, the polyurethane foam of Example 6 containing the flame retardant A and Example 7 containing the flame retardant B have very good flame retardancy compared to that of Comparative Example 4 containing the conventional flame retardant H with an increased amount of addition. Although it has a slightly better flame retardancy than that of Comparative Example 3 containing the flame retardant F of the conventional condensation type flame retardant, it has been found that there is no significant difference.

However, as is apparent from the results in Table 3, the polyurethane foams of Examples 6 and 7 had a significantly reduced glass adhesion, that is, a volatile content of 1/4 or less, compared to those of Comparative Example 3, and contained Gingham is excellent.

(Flame retardance evaluation)

A sample was cut from the obtained foam to perform a flame retardance persistence test under the following conditions.

The sample was placed in a gear oven at a set temperature of 150°C, and exposed for 2, 4, 6, and 8 hours, and then flame retardancy was evaluated in the same manner as in the flame retardancy evaluation.

Moreover, the sample of 0 hours of exposure time used as a reference was also tested similarly.

The results obtained are shown in Table 4 and FIG. 1.

From the results of Table 4 and FIG. 1, the polyurethane foam of Example 6 containing the flame retardant A and Example 7 containing the flame retardant B, the combustion distance is slightly longer even when exposed to high temperature for 8 hours, while It has been found that the polyurethane foam of Comparative Example 3 containing the flame retardant F of the conventional condensation-type flame retardant has a combustion distance of twice as much as before exposure (exposure time 0 hours) when exposed to high temperature for 8 hours. That is, the flame retardants A and B of the present invention can maintain excellent flame retardancy as compared to the flame retardant F, and have excellent flame retardancy.

(Evaluation of Atomic Content Retention Rate)

A sample was cut from the obtained foam to evaluate the retention rate of personnel content under the following conditions.

The sample was put into a gear oven at a set temperature of 80°C for 14 days, and the content of personnel in the sample after 3 days, 7 days, and 14 days after high-temperature exposure was measured according to ASTM D 1091.

Similarly, the sample was placed in a gear oven at a set temperature of 100°C for 7 days, and the content of personnel in the sample after 1 day, 3 days, and 7 days after high temperature exposure was measured according to ASTM D 1091.

In addition, the same sample was measured for the unexposed sample as a reference, and the obtained personnel content was 100%, and the proportion of the personnel content in the sample after high temperature exposure was calculated as the personnel content retention rate.

The results obtained are shown in Table 5 and FIG. 2.

From the results of Table 5 and FIG. 2, the polyurethane foam of Example 6 containing the flame retardant A and Example 7 containing the flame retardant B, even when exposed to a high temperature at 80° C. for a long time, the retention rate of personnel content slightly decreases. The polyurethane foam of Comparative Example 3, which can maintain 95% or more at 14 days of exposure, and contains the flame retardant F of the conventional condensation type flame retardant, shows that the retention rate of personnel content decreases to 86% at 14 days of exposure. Could know. That is, the flame retardants A and B of the present invention have a very low retention rate of personnel compared to the flame retardant F and have a high retention rate.

Moreover, in the same exposure at 100°C for 7 days, the flame retardants A and B have a retention rate of 82% or more of personnel, and a retention rate of higher personnel content than 71% of the flame retardant F.

In the flame retardant F, it is thought that the short-term phosphoric acid ester component contained during exposure to high temperature for a long time is lost due to volatilization or scattering, and as a result, the content of personnel in the foam decreases, and the flame retardance persistence is deteriorated.

On the other hand, since the flame retardants A and B of the present invention have a very small amount of the volatile ester component, which is a volatile component, compared to the flame retardant F, the number of particles lost from the foam is very small, and the retention rate and retention of high flame retardants are excellent. I think.

From the above results, the flame retardant of the present invention and the flame retardant resin composition containing the same exhibit excellent flame retardancy among the required conditions, furthermore, little change over time in durability, excellent fogging resistance, and low volatile content.

Claims (10)

In the flame retardant for a resin containing an organophosphorus compound of the formula (I),
When the organophosphorus compound was measured by gel permeation chromatography (GPC), the content of the compound of n=0 in the following formula (I) is 0.1 to 3.0 area%, and n=0 in the following formula (I) Flame retardant for resins having an average degree of condensation (N) of 1.5 to 3.0 calculated from the content of each compound of -10:

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or a haloalkyl group having 1 to 8 carbon atoms, Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10. The flame retardant for resins according to claim 1, wherein the content of the compound of n=1 in the formula (I) is 10 to 50% by area when the organic phosphorus compound is measured by GPC. The flame retardant for resins according to claim 1, wherein the average condensation degree (N) in the formula (I) is 1.8 to 3.0. A flame retardant resin composition containing the flame retardant for resins according to claim 1 and a resin. The flame retardance according to claim 4, wherein the resin is a resin selected from polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, styrene resin and synthetic rubber. Resin composition. The flame-retardant resin composition according to claim 5, wherein the polyurethane resin is a polyurethane foam. The flame-retardant resin composition according to claim 4, comprising 1 to 40 parts by weight of the flame retardant for the resin relative to 100 parts by weight of the resin. As the step (1), the compound (c) of the compound (a) of the formula (a), the compound (b) of the formula (b), and the compound (c) of the formula (c) per 1 mol of the compound (a) ) In a ratio of 1.5 to 3.5 mol, and further reacting the compound (b) in a proportion of 1.3 to 2.0 mol with respect to 1 mol of the compound (c) at a temperature of -20 to 60 deg. The step of obtaining the compound (d),
Subsequently, as step (2), the compound (d) obtained in step (1) is oxidized with an oxidizing agent, represented by formula (I), and measured by GPC, n=0 in formula (I). A step of obtaining an organic phosphorus compound having an average condensation degree (N) of 1.5 to 3.0, wherein the content of the compound is 0.1 to 3.0 area%, and the content of each compound of n = 0 to 10 in the formula (I) is Method for preparing an organophosphorus compound comprising:

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or a haloalkyl group having 1 to 8 carbon atoms, Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 10, R ₅ is an alkyl group having 1 to 8 carbon atoms or a haloalkyl group, and X is a halogen atom. The method for producing an organophosphorus compound according to claim 8, wherein the content of the compound of n=1 in the formula (I) is 10 to 50% by area when the organophosphorus compound is measured by GPC. The method for producing an organophosphorus compound according to claim 8, wherein the average condensation degree (N) in the formula (I) is 1.8 to 3.0.

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