CN114196022B

CN114196022B - Phosphorus-containing, silicon-containing and sulfonate-containing compound, and preparation method and application thereof

Info

Publication number: CN114196022B
Application number: CN202111631523.2A
Authority: CN
Inventors: 陈俊; 王胜广; 许夕峰; 胡辉; 吴艳青; 朱虹
Original assignee: Fujian Xin'an Technology Co ltd
Current assignee: Fujian Xin'an Technology Co ltd
Priority date: 2021-12-28
Filing date: 2021-12-28
Publication date: 2022-11-29
Anticipated expiration: 2041-12-28
Also published as: CN114196022A

Abstract

The invention provides a compound containing phosphorus, silicon and sulfonate, which has a general formula shown in a formula (I). The compound has excellent thermal stability and carbon forming property, and also has excellent water resistance and flame retardant property, when the compound is added into a polymer composition as an additive, the mechanical property of the polymer composition is not obviously reduced, and transparent or non-transparent flame retardant polymer composition products can be obtained according to the structure of a compound containing phosphorus, silicon and sulfonate groups and the change of preparation raw materials, and the addition amount is lower. The phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the invention is proved to have excellent effect on increasing the flame retardance of a polymer composition, particularly a flame-retardant polymer composition, is particularly suitable for the flame retardance of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardance. The preparation route provided by the invention has the advantages of simple process and strong controllability, and is suitable for industrial production. (R) ¹ _a R ² _g SiO _{(4‑a‑g)/2} ) _n (R ³ _f SiO _(4‑f)/2 ) _q (SiO ₂ ) _m (I)。

Description

Phosphorus-containing, silicon-containing and sulfonate-containing compound, and preparation method and application thereof

Technical Field

The invention belongs to the field of polymer flame retardants, and relates to a phosphorus-containing, silicon-containing and sulfonate-containing compound, a preparation method thereof, and a flame-retardant polymer composition, in particular to a phosphorus-containing, silicon-containing and sulfonate-containing compound, a preparation method thereof, and application thereof in the field of polymer processing.

Background

The polymer materials such as epoxy resin, engineering plastics, polyester and the like are widely applied, but most of the polymer materials are not flame-retardant, and halogen-containing (such as bromine and chlorine) flame retardants are required to be added to ensure that the polymer materials have the fireproof and flame-retardant functions. The high molecular material added with the halogen-containing flame retardant can release a large amount of harmful and toxic substances during combustion. In the years, the green and environment-friendly phosphorus-containing flame retardant, the silicon-containing flame retardant becomes the direction of the research of scientific workers, and in the phosphorus-containing flame retardant, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is the direction of the research of a hot spot as a reactive phosphorus-containing flame retardant intermediate due to the P-H chemical bond contained. The silicon-containing flame retardant not only serves as a hotspot of technical research due to the advantages of higher thermal stability and carbon forming property, but also has mature product sale on the market.

In recent years, there have been related studies and reports on green environmental protection type flame retardants such as phosphorus-containing and silicon-containing flame retardants, silicon-containing and sulfonate-containing flame retardants, phosphorus-containing, silicon-containing and nitrogen-containing flame retardants, phosphorus-containing, nitrogen-containing and sulfonate-containing flame retardants, and the like. For example, patent CN1156539C (2004) discloses a flame-retardant epoxy resin, the structure of the resin contains DOPO group, in the description of the claims, the structure of the resin can contain sulfonic acid group, the patent content does not describe and explain the sulfonic acid group in detail, and the application of the flame-retardant resin is limited to the field of flame-retardant epoxy resin. Patent CN107652468B (2017) discloses an imidazolium sulfonate ionic liquid flame retardant containing a DOPO structure, wherein DOPO and paraformaldehyde react to obtain an intermediate I, then the intermediate I reacts with substituted sulfonyl chloride to obtain an intermediate II, and finally the intermediate II reacts with substituted imidazole to obtain a target product. Patent CN108440598B (2018) discloses a preparation method and application of a sulfur-nitrogen-phosphorus composite flame retardant, maleic anhydride is adopted to react with 2,2-thiobis (5-aminobenzenesulfonic acid), and then the reaction is carried out with DOPO to produce the sulfur-nitrogen-phosphorus composite flame retardant containing DOPO and sulfonic acid structural units, 2,2-thiobis (5-aminobenzenesulfonic acid) raw materials used in the invention are difficult to buy in the market, 4,4' -diaminodiphenyl sulfide required for synthesis is very expensive, and the sulfur-nitrogen-phosphorus composite flame retardant prepared by the method is only suitable for scientific research and difficult to be applied industrially. Patent CN110945066a (2018) discloses a flame retardant and plasticizer-sulfonate and sulfinate for plastics, the flame retardant or plasticizer is halogen-free nitrogen sulfonate alcohol and halogen-free nitrogen sulfinate alcohol ester, which react with substituted sulfonyl chloride and imidazole ring-containing compound to obtain sulfonic acid ester-containing and nitrogen-containing flame retardant products, which can not be used alone when used as a flame retardant, and needs to be compounded with phosphorus-containing flame retardants such as phosphazenes and phosphoric acid esters, and still needs to be added with more phosphorus-containing flame retardants to achieve satisfactory flame retardant effect. The research on synthesis of intumescent sulfonate flame retardant and flame retardant polycarbonate thereof (2014) and the preparation of nitrogen-phosphorus-sulfur composite flame retardant system and the application thereof in polycarbonate (2015) of the university of north and middle schools are realized by taking cyanuric chloride, sulfanilic acid or aminoethanesulfonic acid, potassium hydroxide and DOPO as raw materials to prepare the flame retardant containing phosphorus, nitrogen and sulfonate and containing P-H bonds. Patent EP1865015A1 discloses a polysiloxane flame retardant containing sulfonate group, which is prepared through oxidation-reduction reaction, hydrolysis-condensation reaction and acid-base neutralization reaction of a hydrosulfide-containing and hydrolyzable silicon compound, and is mainly used for flame retardance of polycarbonate and its alloy, and the addition amount of at least 1 wt% is required to achieve the flame retardance effect of ul943.2mmv0, and for other high molecular materials, the flame retardance effect is poor.

Therefore, how to find a suitable compound containing phosphorus, silicon and sulfonate, make up the deficiencies of thermal stability, char formation and flame retardant property, and further widen the depth and width of the application thereof has become one of the most promising first-line researchers in the field.

Disclosure of Invention

In view of the above, the technical problem solved by the present invention is to provide a phosphorus-containing, silicon-containing and sulfonate-containing compound, a preparation method thereof, and a flame retardant polymer composition, wherein the phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the present invention is used as a flame retardant for a polymer material, and has excellent thermal stability, char formation, water resistance and flame retardant property, and particularly has a very high industrial application value in the field of polycarbonate flame retardant.

The invention provides a compound containing phosphorus, silicon and sulfonate, which has a general formula shown in a formula (I);

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

wherein n is greater than 0; q is more than or equal to 0; m is more than or equal to 0;

a is an integer, and a is more than or equal to 4 and more than or equal to 1; g is an integer, 3 is more than or equal to g and more than or equal to 0; and 4 is more than or equal to a + g is more than or equal to 1;

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

each of said R ¹ Each R ² Each R ³ Independently of each other, to a Si atom;

each of said R ² Each R ³ Each independently selected from substituted or unsubstituted C1-C30 alkyl;

the R is ¹ Each independently is selected from structures shown in formula (II) or formula (III);

said M comprises a metal and/or, ammonia/amine compound;

wherein b, j and t are the number of substituents and are selected from integers, b is more than or equal to 8 and more than or equal to 1,4 and more than or equal to 0,4 and more than or equal to t and more than or equal to 0, j + t is more than or equal to 7 and more than or equal to 0, b + t + j is less than or equal to 8;

the R is ⁴ 、R ⁵ Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.

Preferably, the compound comprises a flame retardant;

the compound is a solid;

the M comprises one or more of alkali metal, alkaline earth metal and amino-containing silicon compound;

the alkyl group comprises one or more of straight-chain alkyl, branched-chain alkyl, cyclic alkyl, straight-chain alkenyl, branched-chain alkenyl, aryl and naphthyl;

the mass percentage of the S element in the compound is 0.001-30%;

in the formula (II) or the formula (III), OH is connected with a carbon atom which is ortho-position or meta-position of a P atom.

Preferably, said R is ⁴ And R ⁵ Can form a saturated or unsaturated cyclic ring;

the cyclic ring includes an unsubstituted cyclic ring or a cyclic ring substituted with a C1-C6 alkyl group;

in the formula (I), R ¹ _a R ² _g SiO _(4-a-g)/2 The molar content of the chain link is 10mol percent to 100mol percent;

in the formula (I), R ³ _f SiO _(4-f)/2 The molar content of the chain link is 0mol% -90 mol%;

in the formula (I), siO is ₂ The mol content of the chain link is 0mol% -90 mol%;

and b is 1.

The invention provides a preparation method of a compound containing phosphorus, silicon and sulfonate, which comprises the following steps:

1) Carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);

2) Carrying out addition reaction on the compound containing phosphorus and sulfonic acid groups obtained in the step and a silicon compound containing epoxy groups, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, silicon and sulfonic acid salts with a structure shown in a formula (I);

or:

1') carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);

2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a silicon compound containing an epoxy group to obtain a phosphorus-containing, silicon-containing and sulfonic acid salt-containing compound with a structure shown in a formula (I);

or:

1'), carrying out addition reaction on DOPO or a derivative thereof and a silicon compound containing an epoxy group to obtain a phosphorus-containing and silicon-containing compound intermediate;

2'), carrying out sulfonation reaction on the intermediate of the phosphorus-containing and silicon-containing compound obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate of the phosphorus-containing and silicon-containing compound and a metal compound and/or an ammonia/amine compound to obtain a phosphorus-containing, silicon-containing and sulfonate-containing compound with a structure shown in a formula (I);

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

each of said R ¹ Each R ² Each R ³ Independently of one another, to the Si atom;

said R is ¹ Each independently is selected from structures shown in formula (II) or formula (III);

said M comprises a metal and/or, ammonia/amine compound;

Preferably, the sulfonating agent comprises one or more of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide;

the temperature of the sulfonation reaction is 0-150 ℃;

the sulfonation reaction time is 0.5-10 h.

Preferably, the epoxy group-containing silicon compound includes one or more of a silicon compound represented by the formula (VI), a hydrolysate thereof, and a partial hydrolysis-condensate thereof:

R ⁶ _a R ² _g SiX _(4-a-g) (VI)；

each X is independently bonded to a silicon atom;

said X comprises a halogen and/or a hydrolysable group;

the R is ⁶ Is an organic group containing an epoxy group;

each of said R ⁶ Independently of one another, to the Si atom;

the addition reaction comprises performing the addition reaction under the condition of a catalyst;

the catalyst comprises one or more of an acidic compound, a basic compound and an organic peroxide;

the acidic compound comprises one or more of methylbenzenesulfonic acid, methylnaphthalenesulfonic acid, glacial acetic acid and biphenyl sulfonic acid;

the alkaline compound comprises one or more of sodium hydroxide, potassium hydroxide, ammonia, fatty amine, substituted fatty amine, arylamine, substituted arylamine and amino-substituted alkyl silane;

the organic peroxide comprises one or more of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, cyclohexanone peroxide and methyl ethyl ketone peroxide.

Preferably, said R is ⁶ Including 3- [ (2,3) -glycidoxy]One or more of propyl, 2- (3,4-epoxycyclohexyl) ethyl, and (3-glycidyl) propoxy-substituted heptaisobutyl;

the temperature of the addition reaction is 50-160 ℃;

the time of the addition reaction is 2-20 h;

the raw materials of the addition reaction also comprise an addition reaction solvent;

the addition reaction solvent comprises one or more of benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.

Preferably, the metal compound includes a metal compound that ionizes a metal ion in a solvent;

the metal compound comprises one or more of alkali metal compound, alkaline earth metal compound, aluminum sulfate and aluminum nitrate;

the ammonia/amine compound comprises one or more of ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine and amino-silicon-containing compound;

the amino-containing silicon compound comprises one or more of aminopropyl dimethyl methoxysilane, aminopropyl methyl dimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyl polysiloxane and aminopropyl methyl phenyl polysiloxane.

The invention also provides a flame-retardant polymer composition which comprises the phosphorus-containing, silicon-containing and sulfonate-containing compound in any one of the technical schemes or the phosphorus-containing, silicon-containing and sulfonate-containing compound prepared by the preparation method in any one of the technical schemes.

Preferably, the polymer matrix of the flame retardant polymer composition comprises one or more of polycarbonate, epoxy resin, polyphenylene oxide, polyalkylene terephthalate, vinyl polymer, polyalkylene, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and silicone rubber;

the weight content of the phosphorus-containing, silicon-containing and sulfonate-containing compound in the polymer composition is 0.01-30%;

additives are also included in the polymer composition;

the additive comprises one or more of pigment, UV stabilizer, antioxidant, anti-dripping agent, heat stabilizer, reinforcing filler, chain extender, colorant and flexibilizer;

the phosphorus-containing, silicon-containing and sulfonate-containing compound is used as a flame retardant of a polymer composition, and the polymer composition also comprises other flame retardants or flame retardant systems.

The invention provides a phosphorus-containing, silicon-containing and sulfonate-containing compound which has a structure shown in a formula (I). Compared with the prior art, the invention aims at solving the problems of insufficient thermal stability, carbon forming property, flame retardant property and the like of the existing flame retardant for processing polymers. The invention creatively designs a phosphorus-containing, silicon-containing and sulfonate-containing compound with a specific structure, contains P, si and S three flame-retardant elements, can be used as a flame retardant for flame retardance of high molecular materials, has excellent thermal stability, carbon formation property, water resistance and flame retardance, can not obviously cause the reduction of the mechanical property of a polymer composition when being added into the polymer composition as an additive, and can obtain a transparent or non-transparent flame-retardant polymer composition product according to the structure of the phosphorus-containing, silicon-containing and sulfonate-containing compound and the change of preparation raw materials. The phosphorus-containing, silicon-containing and sulfonate-containing compounds of the present invention have proven to have excellent effects for increasing the flame retardancy of polymer compositions, in particular flame retardant polymer compositions.

In the scientific research process, the research of the invention considers that 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof are sulfonated with a sulfonating agent, then are subjected to addition reaction with silicon compounds containing epoxy groups, and are subjected to neutralization or precipitation reaction with metal compounds and ammonia/amine compounds to obtain the compounds containing phosphorus, silicon and sulfonate. The novel phosphorus, silicon and sulfonate containing compound is obtained by utilizing the characteristics that benzene rings in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof can be sulfonated and P-H bonds can be subjected to addition reaction with silicon compounds containing epoxy groups. The compound contains P, si and S, and can be used as a flame retardant for flame retardance of high polymer materials. The preparation route provided by the invention has the advantages of simple process, strong controllability and easily obtained raw materials, and is particularly suitable for industrial production. The phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the invention has excellent thermal stability and carbon formation, excellent water resistance and flame retardant property, can improve the flame retardant property of the polymer composition, can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardant.

Experimental results show that the phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the invention not only has excellent thermal stability and carbon formation, but also has excellent water resistance and flame retardant property, not only can improve the flame retardant property of the polymer composition, but also can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, and the addition amount is lower.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.

All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity conventionally used in the field of analytical purification or preparation of polymer flame retardants.

All noun expressions, acronyms and designations of the invention belong to the general noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expression, acronyms and designations.

The invention provides a compound containing phosphorus, silicon and sulfonate, which is characterized by having a general formula shown in a formula (I);

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

said M comprises a metal and/or, ammonia/amine compound;

In the present invention, n > 0; q is more than or equal to 0; m is more than or equal to 0. The upper limit of n, q and m in the present invention is not particularly limited, and those skilled in the art may adjust based on common sense, demand and performance.

In the present invention, the numbers of a, g and f are preferably integers. Specifically, a is more than or equal to 4 and is more than or equal to 1, and specifically, the a can be 1,2,3 or 4. G is more than or equal to 3 and is more than or equal to 0, and specifically is 0,1,2 or 3. The sum of a and g is more than or equal to 4 and is more than or equal to 1, and specifically can be 1,2,3 or 4. F is more than or equal to 3 and is more than or equal to 1, and specifically can be 1,2 or 3.

In the present invention, each of R is ¹ Each R ² Each R ³ Independently of each other, to the Si atom. Wherein each R is ² Each R ³ Each independently selected from substituted or unsubstituted C1-C30 hydrocarbyl. Specifically, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 5 to 25 carbon atoms, and more preferably a hydrocarbon group having 10 to 20 carbon atoms. More specifically, the hydrocarbon group preferably includes one or more of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, an aryl group, and a naphthyl group, and more preferably a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, an aryl group, or a naphthyl group。

In the present invention, said R ¹ Each independently is selected from structures shown in formula (II) or formula (III);

wherein b, j and t are the number of substituents and are selected from integers, 8 is more than or equal to b and more than or equal to 1,4 and more than or equal to j and more than or equal to 0,4 and more than or equal to t and more than or equal to 0, 7 is more than or equal to j + t and more than or equal to 0, b + t + j is less than or equal to 8;

in the present invention, the-OH group in the formula (II) or the formula (III) is bonded to a carbon atom which is ortho-or meta-to the P atom.

In the present invention, the number of the substituents b, j, and t is preferably an integer. Specifically, the b is more than or equal to 8 and is more than or equal to 1, and specifically, the b can be 1,2,3,4,5,6,7 or 8. J is more than or equal to 4 and is more than or equal to 0, and can be 0,1,2,3 or 4. T is more than or equal to 4 and is more than or equal to 0, and particularly can be 0,1,2,3 or 4. The sum of j and t is more than or equal to 7 and is more than or equal to 0, and can be 0,1,2,3,4,5,6 or 7. The a + b + c is less than or equal to 8, and can be 1,2,3,4,5,6,7 or 8. Among them, b is more preferably 1 or 2, and most preferably 1.

In the present invention, said M comprises a metal and/or an ammonia/amine compound, more preferably a metal or ammonia/amine compound group. In the present invention, the ammonia/amine compound represents an independent material name.

In the present invention, the M preferably includes one or more of an alkali metal, an alkaline earth metal and an amino-containing silicon compound, more preferably an alkali metal, an alkaline earth metal or an amino-containing silicon compound group, further preferably sodium and potassium, and most preferably potassium.

In the present invention, said R ⁴ 、R ⁵ Each independently is preferably one or more selected from halogen, nitro, C1-C15 alkyl and C1-C15 alkoxy, more preferably halogen, nitro, C1-C15 alkyl or C1-C15 alkoxy. Specifically, the alkyl group having 1 to 15 carbon atoms may be an alkyl group having 3 to 12 carbon atoms, an alkyl group having 5 to 10 carbon atoms, or an alkyl group having 7 to 9 carbon atoms. The C1-C15 alkoxy can be C3-C12 alkoxy, orIs C5-C10 alkoxy, or C7-C9 alkoxy.

In the present invention, said R ⁴ And R ⁵ Preferably, a saturated or unsaturated cyclic ring can be formed. Namely R ⁴ And R ⁵ Preferably, a saturated ring structure or an unsaturated ring structure may be formed.

In the present invention, the cyclic ring preferably includes an unsubstituted cyclic ring or a cyclic ring substituted with a C1 to C6 alkyl group. Specifically, the alkyl group having 1 to 6 carbon atoms may be an alkyl group having 2 to 5 carbon atoms or an alkyl group having 3 to 4 carbon atoms.

In the present invention, the content of the S element in the compound is preferably 0.001% to 30% by mass, more preferably 0.01% to 25% by mass, more preferably 0.1% to 20% by mass, more preferably 0.1% to 15% by mass, and more preferably 0.1% to 10% by mass.

In the present invention, in the formula (I), R ¹ _a R ² _g SiO _(4-a-g)/2 The molar content of the chain units is preferably from 10mol% to 100mol%, more preferably from 30mol% to 80mol%, more preferably from 50mol% to 60mol%.

In the present invention, in the formula (I), R ³ _f SiO _(4-f)/2 The molar content of the chain units is preferably from 0mol% to 90mol%, more preferably from 10mol% to 70mol%, and still more preferably from 30mol% to 50mol%.

In the present invention, in the formula (I), siO is used ₂ The molar content of the chain units is preferably from 0mol% to 90mol%, more preferably from 10mol% to 70mol%, and still more preferably from 30mol% to 50mol%.

In the present invention, the state of the compound is preferably a solid.

In the present invention, the compound preferably includes a flame retardant.

The above steps of the present invention provide a phosphorus, silicon and sulfonate containing compound having a specific structure.

The phosphorus-containing, silicon-containing and sulfonate compound comprises a compound shown as a formula (I):

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (Si0 ₂ ) _m (I)。

in the formula (I), n is more than 0; q is more than or equal to 0; m is more than or equal to 0.a is an integer, and a is more than or equal to 4 and more than or equal to 1; g is an integer, and 3 is more than or equal to g and more than or equal to 0;4 is more than or equal to a and g is more than or equal to 1; f is an integer, and f is more than or equal to 3 and more than or equal to 1.

In the present invention, H may be included in the definition of the monovalent form group.

Wherein each R is ¹ The monovalent group bonded to the Si atom independently includes a structure represented by the formula (II) and/or a structure represented by the formula (III).

In the present invention, the sulfonate (-SO) in the formula (II), the formula (III) ₃ The S elements in the M) groups are independently connected with carbon on a benzene ring, the content of the sulfonate cannot be too high, otherwise the hydrophilicity or water solubility of the product can be greatly increased, if the content is too low, the flame retardant property of the product is influenced, and the S elements preferably account for 0.001-30% by mass of the compound in the formula (I), and further preferably account for 0.1-10% by mass of the compound in the formula (I).

In the present invention, each of R is ⁴ ，R ⁵ Each independently of the others, is selected from the group consisting of monovalent radicals comprising H, halogen (F, cl, br, I), nitro, C1-C15 alkyl, C1-C15 alkoxy or R ⁴ And R ⁵ Taken together, may form a saturated or unsaturated cyclic ring, wherein the saturated or unsaturated cyclic ring may be optionally substituted with a C1-C6 alkyl group.

In the present invention, M is selected from metals, ammonia/amine compounds, preferably alkali metals, alkaline earth metals, amino-containing silicon compounds, more preferably sodium and potassium, and most preferably potassium.

In the present invention, b is an integer of 8. Gtoreq.b.gtoreq.1, preferably b =1,2, and more preferably b =1; j and t are integers, and j is more than or equal to 4 and is more than or equal to 0,4 and more than or equal to t and is more than or equal to 0; j + t is more than or equal to 7 and more than or equal to 0; b + t + j =8.

In the present invention, each of R is ² Each R ³ Independently of one another, to the Si atom. Specifically, each of R ² ，R ³ Monovalent organic groups bonded to the Si atom independently of each other. Preferably, each R ² ，R ³ Independently of one another, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, such as a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms; a straight-chain or branched alkenyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms; aryl optionally substituted with the above alkyl such as phenyl, naphthyl; the above alkyl groups optionally substituted with an aryl group such as phenyl. Specifically, some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms (fluorine, chlorine, bromine, iodine) and/or acryloxy, methacryloxy, epoxy, glycidyloxy, carboxyl, hydroxyl, mercapto, amino, sulfonic acid, nitro, amine groups, including but not limited to: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, aralkyl groups such as benzyl and phenethyl, alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl, and heptenyl, and cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl. Preferably R ² ，R ³ 50% by mol or more of methyl group, phenyl group and vinyl group, more preferably 50% by mol or more of methyl group and phenyl group, most preferably 50% by mol or more of phenyl group. According to R ² ，R ³ Various functional phosphorus-containing, silicon-containing and sulfonate-containing compounds can be prepared according to different groups, such as: and a functional group such as phenyl, amino, epoxy, mercapto, sulfonic acid, alkenyl, propenyloxy, and the like.

or:

1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);

or:

1'), carrying out addition reaction on DOPO or derivatives thereof and silicon compounds containing epoxy groups to obtain phosphorus-containing and silicon-containing compound intermediates;

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

said M comprises a metal and/or, ammonia/amine compound;

2) And (2) carrying out addition reaction on the compound containing phosphorus and sulfonic acid group obtained in the step and a silicon compound containing epoxy group, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain the compound containing phosphorus, silicon and sulfonic acid salt with the structure shown in the formula (I).

Note that, in the present invention, DOPO or its derivative represents an independent material name; the phosphorus-and sulfonic acid group-containing compounds represent independent material names; the epoxy group-containing silicon compound (epoxy group-containing and silicon-containing compound) represents an independent material name; metal compounds represent independent material names; ammonia/amine compounds represent independent material names; the phosphorus, silicon and sulfonate containing compounds represent independent material names.

According to the invention, DOPO or a derivative thereof and a sulfonating agent are subjected to sulfonation reaction to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V).

In the present invention, the sulfonating agent preferably includes one or more of concentrated sulfuric acid, oleum, chlorosulfonic acid and sulfur trioxide, more preferably concentrated sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.

In the present invention, the temperature of the sulfonation reaction is preferably 0 to 150 ℃, more preferably 30 to 120 ℃, and more preferably 60 to 90 ℃.

In the present invention, the sulfonation reaction time is preferably 0.5 to 10 hours, more preferably 2 to 8 hours, and still more preferably 4 to 6 hours. In the present invention, the time of the sulfonation reaction differs depending on the kind of the sulfonating agent and the reaction solvent.

The phosphorus-containing and sulfonic acid group-containing compound obtained in the step is subjected to addition reaction with a silicon compound containing an epoxy group, and then subjected to neutralization or precipitation reaction with a metal compound and/or an ammonia/amine compound to obtain the phosphorus-containing, silicon-containing and sulfonic acid salt-containing compound with the structure shown in the formula (I).

In the present invention, the epoxy group-containing silicon compound preferably contains one or more of a silicon compound represented by the formula (VI), a hydrolysate thereof, a partial hydrolysis-condensate thereof:

R ⁶ _a R ² _g SiX _(4-a-g) (VI)。

wherein each X is preferably independently bonded to a silicon atom. The X preferably comprises a halogen and/or a hydrolysable group, more preferably a halogen or a hydrolysable group. Each of said R ⁶ Preferably independently of each other, to the Si atom. Said R is ⁶ Preferably an organic group containing an epoxy group, more preferably a monovalent hydrocarbon group containing an epoxy group. Specifically, the R is ⁶ Preferably comprising 3- [ (2,3) -glycidoxy]One or more of propyl, 2- (3,4-epoxycyclohexyl) ethyl and (3-glycidyl) propoxy-substituted heptaisobutyl, more preferably 3- [ (2,3) -epoxypropoxy]Propyl, 2- (3,4-epoxycyclohexyl) ethyl or (3-glycidyl) propoxy-substituted heptaisobutyl.

More specifically, the epoxy group-containing silicon compound preferably includes 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldiethoxysilane, (3-glycidoxy) propyltrimethoxysilane, (3-glycidoxy) propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- [ (2,3) -glycidoxy ] propyltrimethoxysilane, 1,3-bis (3-glycidyloxypropyl) tetramethyldisiloxane, glycidoxypropyl-POSS.

In the present invention, said R ⁶ After the addition reaction with P-H, the P atom of the DOPO and the derivative thereof is connected.

In the present invention, the addition reaction preferably includes conducting the addition reaction under the condition of a catalyst.

In the present invention, the catalyst preferably includes one or more of an acidic compound, a basic compound and an organic peroxide, and more preferably an acidic compound, a basic compound or an organic peroxide.

In the present invention, the acidic compound preferably includes one or more of methylbenzenesulfonic acid, methylnaphthalenesulfonic acid, glacial acetic acid, and biphenylsulfonic acid, and more preferably methylbenzenesulfonic acid, methylnaphthalenesulfonic acid, glacial acetic acid, or biphenylsulfonic acid.

In the present invention, the basic compound preferably includes one or more of sodium hydroxide, potassium hydroxide, ammonia, a fatty amine, a substituted fatty amine, an aromatic amine, a substituted aromatic amine, and an amino-substituted alkylsilane, and more preferably, sodium hydroxide, potassium hydroxide, ammonia, a fatty amine, a substituted fatty amine, an aromatic amine, a substituted aromatic amine, or an amino-substituted alkylsilane.

In the present invention, the organic peroxide preferably includes one or more of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, cyclohexanone peroxide and methyl ethyl ketone peroxide, and more preferably dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, cyclohexanone peroxide or methyl ethyl ketone peroxide.

In the present invention, the temperature of the addition reaction is preferably 50 to 160 ℃, more preferably 70 to 140 ℃, and still more preferably 90 to 120 ℃.

In the present invention, the time for the addition reaction is preferably 2 to 20 hours, more preferably 5 to 17 hours, and still more preferably 8 to 14 hours.

In the present invention, the raw materials for the addition reaction preferably include an addition reaction solvent.

In the present invention, the addition reaction solvent preferably includes one or more of benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, and N, N-dimethylformamide, and more preferably benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, or N, N-dimethylformamide.

In the present invention, the metal compound preferably includes a metal compound that ionizes a metal ion in a solvent.

In the present invention, the metal compound preferably includes one or more of an alkali metal compound, an alkaline earth metal compound, aluminum sulfate, and aluminum nitrate, and more preferably an alkali metal compound, an alkaline earth metal compound, aluminum sulfate, or aluminum nitrate.

In the present invention, the ammonia/amine-based compound preferably includes one or more of ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, and amino-containing silicon-based compound, and more preferably ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, or amino-containing silicon-based compound.

In the present invention, the amino-containing silicon compound preferably includes one or more of aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane and aminopropylmethylphenylpolysiloxane, and more preferably aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane or aminopropylmethylphenylpolysiloxane.

The invention also provides a preparation method of the compound containing phosphorus, silicon and sulfonate, and the other two preparation routes comprise:

1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);

2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a silicon compound containing an epoxy group to obtain the phosphorus-containing, silicon-containing and sulfonic acid salt-containing compound with the structure shown in the formula (I).

Or:

2'), carrying out sulfonation reaction on the intermediate of the phosphorus-containing and silicon-containing compound obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate of the phosphorus-containing and silicon-containing compound and a metal compound and/or an ammonia/amine compound to obtain the phosphorus-containing, silicon-containing and sulfonate-containing compound with the structure shown in the formula (I).

In the present invention, the raw material selection, the specific reaction process and the process parameters in the two preparation routes, and the corresponding preferred principles thereof, may correspond to the raw material selection, the specific reaction process and the process parameters in the first preparation route, and the corresponding preferred principles thereof one by one, and are not described in detail herein.

The invention is a complete and detailed integral technical scheme, better ensures the structure and performance of the phosphorus-containing, silicon-containing and sulfonate-containing compounds, further improves the comprehensive performance of the phosphorus-containing, silicon-containing and sulfonate-containing compounds, such as flame retardance, and the like, and the preparation method of the phosphorus-containing, silicon-containing and sulfonate-containing compounds can specifically comprise the following steps:

the compound of formula (I) of the present invention comprises the following preparation method:

(1) The compound is prepared by carrying out sulfonation reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent to generate a compound containing phosphorus and sulfonic acid groups shown in a formula (IV) and/or a formula (V), then carrying out addition reaction on the compound, hydrolysate or partial hydrolysis-condensation product of the compound and the like containing epoxy groups, and finally carrying out neutralization or precipitation reaction on the compound, the hydrolysate or partial hydrolysis-condensation product of the compound and the like.

(2) The compound is prepared by carrying out sulfonation reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent to generate a compound containing phosphorus and sulfonic acid groups shown in a formula (IV) and/or a formula (V), then carrying out neutralization or precipitation reaction on the compound and a metal compound and an ammonia/amine compound, and finally carrying out addition reaction on the compound and a silicon compound containing an epoxy group, a hydrolysate thereof or a partial hydrolysis-condensation product thereof.

(3) The compound is prepared by performing addition reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and silicon compounds containing epoxy groups, hydrolysates thereof or partial hydrolysis-condensation products thereof to obtain phosphorus-containing and silicon-containing compound intermediates, then performing sulfonation reaction on the phosphorus-containing and silicon-containing compound intermediates and a sulfonating agent, and finally performing neutralization or precipitation reaction on the phosphorus-containing and silicon-containing compound intermediates and metal compounds and ammonia/amine compounds.

In the formula (IV) and (V), each R is ⁴ ，R ⁵ And b, j, t are the same as described above.

In the present invention, the production methods (1) and (2) are preferred, and the production method (1) is more preferred.

The 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof, preferably DOPO, are described in the invention.

The compounds of formula (IV) and formula (V) of the present invention can be interconverted under certain conditions, similar to the structural interconversion of DOPO and its hydrolysates. For example, the compound of formula (IV) can be hydrolyzed into the compound of formula (V) under water and certain temperature conditions, and the compound of formula (V) is dehydrated under certain temperature and pressure conditions and converted into the compound of formula (IV). Further preferred according to the invention are compounds of formula (IV).

The epoxy group-containing silicon compound of the present invention comprises a silicon compound represented by the formula (VI), a hydrolysate, a partial hydrolysis-condensate thereof, and a mixture thereof:

R ⁶ _a R ² _g SiX _(4-a-g) (VI)。

each of said R ² A, g are the same as described above; the X is bonded to the silicon atom, and represents a halogen atom such as chlorine, or represents a hydrolyzable group such as an alkoxy group, acyloxy group or the like, further preferably an alkoxy group. Each of said R ⁶ Monovalent organic groups which are bonded to the Si atom independently of one another and contain epoxy groups, preferably each R ⁶ Independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 30 and containing an epoxy group, such as a branched hydrocarbon group (including cyclic hydrocarbon groups) and a linear hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms; phenyl, naphthyl optionally substituted with the above-mentioned hydrocarbon groups and straight chain hydrocarbon groups; the above-mentioned branched and straight chain hydrocarbon groups optionally substituted with an aryl group such as a phenyl group; some or all of the hydrogen atoms bonded to the carbon atoms of the above groups are substituted with halogen atoms (fluorine, chlorine, bromine, iodine) and/or epoxy, glycidyloxy, carboxyl, hydroxyl, mercapto, amino, nitro, amino groups, including but not limited to: 3- [ (2,3) -glycidoxy]Propyl, 2- (3,4-epoxycyclohexyl) ethyl, (3-glycidyl) propoxy-substituted heptaisobutyl, and the like. The R is ⁶ After the addition reaction with P-H, the compound is connected with the P atom of the DOPO and the derivative thereof. Further, the amount of the silicon compound represented by the formula (VI) to be added is not particularly limited, and is preferably in a range satisfying the addition reaction of P-H in DOPO and its derivatives, for example, in a range of a molar ratio of an epoxy group to P-H: (1-1.5): 1, further preferably 1.2:1, more preferably 1.02:1.

the epoxy group-containing silicon compound of the present invention is, for example, selected from, but not limited to: 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldiethoxysilane, (3-glycidoxy) propyltrimethoxysilane, (3-glycidoxy) propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- [ (2,3) -glycidoxy ] propyltrimethoxysilane, 1,3-bis (3-glycidyloxypropyl) tetramethyldisiloxane, glycidoxypropyl-POSS.

In the formula (I), R is ³ _f SiO _(4-f)/2 Chain links, independently of one another, consisting of R ³ _f SiX _(4-f)/2 The silicon compound is generated after hydrolysis-condensation; the SiO ₂ Chain links, independently of one another, of SiX ₄ The silicon compound is produced by hydrolysis-condensation, and R is ³ F, X are each independently of the other as defined above. When the silicon compound of formula (VI) contains a hydrolyzable-condensable group, it may react with said R ³ _f SiX _(4-f)/2 ，SiX ₄ Silicon compounds, combined by means of cohydrolysis-condensation reactions, to give compounds containing R ¹ _a R ² _g SiO _(4-a-g)/2 ，R ³ _f SiO _(4-f)/2 ，SiO ₂ A mer compound or a mixture thereof. When the silicon compound of the formula (VI) is free of hydrolyzable-condensing groups, then ¹ _a R ² _g SiO _(4-a-g)/2 The compound of (1) and the compound R ³ _f SiX _(4-f)/2 ，SiX ₄ The hydrolysis-condensates of the silicon compounds are combined in a blended manner.

In the present invention, R is ¹ _a R ² _g SiO _(4-a-g)/2 ，R ³ _f SiO _(4-f)/2 ，SiO ₂ The molar ratio of the mer in the compound represented by the formula (I) can be determined by analyzing the raw materials remaining in the reaction system by detection means such as liquid chromatography, gas chromatography, mass spectrometry, etc., or other known detection methods in the art can be used.

In the formula (I), R is ¹ _a R ² _g SiO _(4-a-g)/2 ，R ³ _f SiO _(4-f)/2 ，SiO ₂ The proportion of each chain link is as follows:

R ¹ _a R ² _g SiO _(4-a-g)/2 chain link: 10. The method of the present invention E-mail100mol%, preferably 30 to 100mol%, more preferably 50 to 100mol%.

R ³ _f SiO _(4-f)/2 Chain link: 0 to 90mol%, preferably 10 to 70mol%, more preferably 30 to 50mol%.

SiO ₂ Chain link: 0 to 90mol%, preferably 10 to 70mol%, more preferably 10 to 50mol%.

In the present invention, the sulfonation is one of reaction means commonly used in industrial production, and reference is made to the technical manual of synthesis of fine organic unit reaction, which is compiled by Zhang Daguo.

In the present invention, there is no particular requirement for the selection of the sulfonating agent, such as sulfuric acid (concentrated) at a concentration of 93% or more, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, preferably concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, further preferably concentrated sulfuric acid, chlorosulfonic acid, and most preferably chlorosulfonic acid. In the present invention, there is no particular requirement on the sulfonation temperature, and the sulfonation temperature may be carried out at a temperature lower than 60 ℃ or higher than 120 ℃, and the temperature cannot be too low, which would affect the sulfonation reaction rate, and too high a temperature would cause excessive sulfonation, oxidation, sulfone and resin formation, and other side reactions, but allow the presence of partial oxidation, sulfone and resin in the phosphorus-containing, silicon-containing and sulfonate-containing compounds of the present invention. In the present invention, when concentrated sulfuric acid or fuming sulfuric acid is used as the sulfonating agent, water is also generated during the sulfonation reaction due to the water contained in the sulfonating agent, and the presence of water can hydrolyze part of DOPO and its derivatives completely or partially to produce the compounds represented by the formulae (IV) and (V), and mixtures thereof. The amount of sulfonating agent used is not particularly limited, and is preferably such that at least one sulfonic acid group is generated in one molecule of DOPO and its derivatives.

In the present invention, when the addition reaction of the compound represented by the above formula (IV), formula (V) or a mixture thereof as a raw material with the silicon compound represented by the formula (VI), a hydrolysate, a partial hydrolysis-condensation product thereof or a mixture thereof is carried out, the reaction solvent is not particularly required, and may be optionally added or not added depending on the reaction system, for example, the reaction solvent is added: benzene, toluene, xylene, dichloromethane, methanol, ethanol, isopropanol,N-butanol, acetone, etc., preferably toluene, methanol, ethanol, isopropanol, more preferably methanol, ethanol. Sometimes, in order to shorten the reaction time and simplify the preparation process, the hydrolyzable silicon compound of the formula (VI) is subjected to an autohydrolysis-condensation reaction with the silicon compound of the formula (VI) or the hydrolyzable silicon compound of the formula (VI) and R while adding water to the reaction solvent to form an organic solvent-water system ³ _f SiX _(4-f)/2 ，SiX ₄ A hydrolyzable silicon compound of the formula (VI), R if the silicon compound of the formula (VI) is free of hydrolyzable groups ³ _f SiX _(4-f)/2 ，SiX ₄ The hydrolyzable silicon compound shown undergoes a self-hydrolysis-condensation reaction, and the product thereof is mixed in a blended form with the above addition product.

The product obtained by the invention allows the existence of partial incomplete hydrolysis-condensation groups, such as alkoxy, hydroxyl and the like. The amount of water is not particularly limited so long as it is an amount that allows the above hydrolyzable silicon compound to undergo hydrolysis-condensation reaction.

In the present invention, there is no particular requirement for the type and amount of the catalyst for the addition reaction, such as: acidic compounds such as methylbenzenesulfonic acid, methylnaphthalenesulfonic acid, glacial acetic acid, and diphenylsulfonic acid, and basic compounds such as sodium hydroxide, potassium hydroxide, ammonia, fatty amines, substituted fatty amines, aromatic amines, substituted aromatic amines, and amino-substituted alkylsilanes; organic peroxides such as dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, cyclohexanone peroxide, methyl ethyl ketone peroxide, etc., and more preferably organic peroxides; the amount, for example the weight percentage of the compounds taking part in the reaction monomers, is in the range from 0.01 to 6%, preferably from 0.1 to 2%, more preferably from 0.5 to 1.5%. In the invention, because DOPO and the derivative thereof carry-SO after sulfonation reaction, the intermediate product ₃ H group, which has an autocatalytic effect, and is also a hydrolysis-condensation catalyst of a silicon compound having a hydrolyzable group. According to the actual situation, canOptionally with or without catalyst. When basic compounds are used as catalysts, they can be used on the one hand for-SO ₃ Neutralization of the H groups can be used, on the one hand, for the ring-opening addition reaction of the epoxide groups, if R is added at the same time ³ _f SiX _(4-f)/2 ，SiX ₄ The hydrolyzable silicon compound shown, and also a hydrolysis-condensation catalyst thereof. Further, the reaction temperature is not particularly limited so that the addition reaction of the P-H bond with the epoxy group can be carried out.

In the present invention, the compounds represented by the above formulae (IV) and (V) and mixtures thereof are subjected to addition reaction with the silicon compound represented by the formula (VI), a hydrolysate thereof, a partial hydrolysis-condensation product thereof, and mixtures thereof to obtain an intermediate of a compound containing phosphorus, silicon, and sulfonic acid groups, and the intermediate may be further separated or not extracted.

In the present invention, the metal compound is preferably a metal compound capable of ionizing a metal ion in a solvent, such as: alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium chloride and potassium chloride, alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, calcium chloride, barium chloride, magnesium chloride and magnesium nitrate, and divalent or higher metal ion compounds such as: aluminum sulfate, aluminum nitrate, and the like. The ammonia or amine compound may be, for example, ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, or the like, or an amino-containing silicon compound such as aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane, aminopropylmethylphenylpolysiloxane, or the like. In the present invention, alkaline compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aminopropyltriethoxysilane and the like are more preferable, and potassium hydroxide is more preferable.

In the present invention, the basic compound is not only used for neutralization of sulfonic acid group, but also R ³ _f SiX _(4-f)/2 ，SiX ₄ The hydrolysis-condensation catalyst for hydrolyzable silicon compounds, e.g. phosphorus-, silicon-and sulfonic acid group-containing intermediates, is also the intermediate with R ³ _f SiX _(4-f)/2 ，SiX ₄ The cohydrolysis-condensation catalyst for the hydrolyzable silicon compound shown is not particularly limited in the form of addition, and is generally added in the form of water, an organic solvent (such as an alcohol solvent) or an organic solvent-aqueous solution at a concentration such that the reaction system has a pH of more than 7, preferably more than 9, and further preferably more than 10.

In the present invention, the neutralization reaction refers to an acid-base neutralization reaction between a basic compound and a compound represented by the formula (IV) or (V) of the present invention. In the present invention, the precipitation reaction is specifically defined by the metal compound, ammonia or amine compound, the compound represented by the formula (IV) or (V), the compound represented by the formula (VI), R ³ _f SiX _(4-f)/2 ，SiX ₄ The physical and chemical properties (such as thermal stability, water resistance, whether the mechanical property and transparency of the flame-retardant material are affected or not) of the obtained compound shown in the formula (I) are different from each other, and the solubility of the compound in the reaction system is different, some products can be directly separated from the reaction system in a precipitation mode, sometimes the products need to be separated from the reaction system in a crystallization or recrystallization mode, and the crystallization or recrystallization method is a method well known in the chemical industry. In addition, the compounds represented by the formulae (IV) and (V) contain-SO ₃ H radical, which is itself also R ³ _f SiX _(4-f)/2 ，SiX ₄ A hydrolysis-condensation catalyst of the silicon compound shown.

In the present invention, the structure of the phosphorus-containing, silicon-containing and sulfonate-containing compound represented by formula (I) is not a single structure, the deletion of any structure or different combinations of synthetic raw materials, the variation of the contents of metal elements and S elements (generally referred to as S element in sulfonate structure) and the like, and the properties of the obtained compound represented by formula (I) in flame retardancy, water solubility, melting temperature and mechanical properties and transparency of the obtained flame retardant material may also vary, and the present inventors have described and illustrated in detail in the following examples as much as possible, and it should be understood by those skilled in the art that the scope of the present invention is not limited to the examples of the present invention.

The invention provides a flame-retardant polymer composition, which comprises a phosphorus-containing, silicon-containing and sulfonate-containing compound in any one of the technical schemes or a phosphorus-containing, silicon-containing and sulfonate-containing compound prepared by the preparation method in any one of the technical schemes.

In the present invention, the polymer matrix is exemplified by, but not limited to: vinyl polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyalkenes such as polyethylene, polypropylene, polyalkylene terephthalates such as polybutylene terephthalate, polyethylene terephthalate, polyacrylates such as polymethyl acrylate, polymethacrylates such as polymethyl methacrylate, polyphenylene ethers, polysulfones, polycarbonates, polystyrenes, especially high impact polystyrene, polyamides such as nylon 6, nylon 66, polyimides, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, acrylonitrile-butadiene-styrene copolymer/polycarbonate blends, polystyrene/polyphenylene ether blends, thermoplastic polyester/polycarbonate blends such as butylene terephthalate/polycarbonate blends, silicone rubbers, epoxy resins and mixtures thereof.

In the present invention, the content by weight of the phosphorus-containing, silicon-containing and sulfonate-containing compound in the polymer composition is preferably 0.01% to 30%, more preferably 0.1% to 10%, and still more preferably 0.1% to 6%.

In the present invention, additives are preferably included in the polymer composition.

In the present invention, the additive preferably includes one or more of a pigment, a UV stabilizer, an antioxidant, an anti-dripping agent, a heat stabilizer, a reinforcing filler, a chain extender, a colorant, and a toughening agent, and more preferably a pigment, a UV stabilizer, an antioxidant, an anti-dripping agent, a heat stabilizer, a reinforcing filler, a chain extender, a colorant, or a toughening agent.

In the present invention, the phosphorus-containing, silicon-containing and sulfonate-containing compounds are used as flame retardants for polymer compositions, which preferably include other flame retardants or flame retardant systems.

The present invention provides the above-mentioned polymer composition comprising at least one polymer matrix in which the phosphorus-containing, silicon-containing, and sulfonate-containing compounds of the present invention are dispersed.

According to the invention, any conventional additive may be added to the polymer composition, such as: pigment, UV stabilizer, antioxidant, anti-dripping agent, heat stabilizer, reinforcing filler, chain extender, colorant, toughening agent and the like.

The polymer composition according to the invention preferably also contains a flame retardant, i.e. a polymer composition which is preferably flame retardant. The flame retardant polymer composition has improved processability, dispersibility, flame retardancy and mechanical properties. There is no particular limitation on the flame retardant, and any known flame retardant system for polymer compositions may be used. The flame retardants used in the polymer compositions can be used singly or in combination, for example, halogenated aromatic compounds, especially brominated compounds, and antimony oxide, which have a synergistic flame retardant effect.

Specifically, the polymer composition is extruded, injection molded, blow molded, vulcanized, etc. to obtain an article.

The polymer composition may be prepared by any known method of mixing the components. Generally, there are two distinct mixing steps: premixing and melt mixing. The premixing is to mix the dry components, and generally adopt a tumbler mixer or a ribbon blender for premixing, if necessary, a high shear mixer can be used for preparing the premix; after premixing, it is usually melt mixed. The components of the raw materials may also be added directly to the feed section of the melt mixing device without a premixing step. In melt mixing, the polymer composition components are typically melt blended in a single or twin screw extruder, extruded and cut into moldings, such as conventional pellets, granules, and the like, using standard techniques. The composition is then molded in any equipment conventionally used for molding, such as in an injection molding machine.

The compound containing phosphorus, silicon and sulfonate groups provided by the invention not only has good thermal stability and carbon formation, but also has excellent water resistance and flame retardant property, when the compound is added into a polymer composition as an additive, the mechanical property of the polymer composition is not obviously reduced, and a transparent or non-transparent flame retardant polymer composition product can be obtained according to the structure of the compound containing phosphorus, silicon and sulfonate groups and the change of preparation raw materials.

The phosphorus-containing, silicon-containing, and sulfonate-containing compounds provided by the present invention have proven to be particularly useful for increasing the flame retardancy of polymer compositions, particularly flame retardant polymer compositions. The compound can improve the flame retardant property of the polymer composition, provide better thermal stability and carbon forming property, can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, and is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof.

The invention provides a phosphorus-containing, silicon-containing and sulfonate-containing compound, a preparation method thereof and application thereof in the field of polymer processing. The compound containing phosphorus, silicon and sulfonate with a specific structure simultaneously contains P, si and S three flame retardant elements, can be used as a flame retardant for flame retardance of high polymer materials, has excellent thermal stability and carbon formation property, and also has excellent water resistance and flame retardant property, when the compound is added into a polymer composition as an additive, the mechanical property of the polymer composition cannot be obviously reduced, and a transparent or non-transparent flame retardant polymer composition product can be obtained according to the structure of the compound containing phosphorus, silicon and sulfonate and the change of preparation raw materials. The phosphorus-containing, silicon-containing and sulfonate-containing compounds of the present invention have proven to have excellent effects for increasing the flame retardancy of polymer compositions, in particular flame retardant polymer compositions.

In the scientific research process, the research of the invention considers that 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof are sulfonated with a sulfonating agent, then are subjected to addition reaction with silicon compounds containing epoxy groups, and are subjected to neutralization or precipitation reaction with metal compounds and ammonia/amine compounds to obtain the compounds containing phosphorus, silicon and sulfonate. The novel phosphorus, silicon and sulfonate containing compound is obtained by utilizing the characteristics that benzene rings in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof can be sulfonated and P-H bonds can be subjected to addition reaction with silicon compounds containing epoxy groups. The preparation route provided by the invention has the advantages of simple process, strong controllability and easily obtained raw materials, and is particularly suitable for industrial production. The phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the invention has excellent thermal stability and carbon formation, excellent water resistance and flame retardant property, can improve the flame retardant property of the polymer composition, can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardant.

Experimental results show that the phosphorus-containing, silicon-containing and sulfonate-containing compound provided by the invention not only has excellent thermal stability and carbon formation, but also has excellent water resistance and flame retardant property, can improve the flame retardant property of the polymer composition, can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, and has lower addition amount.

To further illustrate the present invention, the following examples are provided to describe in detail a phosphorus, silicon and sulfonate containing compound, a method for preparing the same, and a flame retardant polymer composition, but it should be understood that these examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.

In the invention, the content of the S element in the phosphorus, silicon and sulfonate containing compound is measured by adopting an ultraviolet fluorescence sulfur detector (model WMTS-5000), the notch impact strength of the simply supported beam of the polymer composition is measured according to the ISO179 standard, the combustion test is carried out according to the method specified by the UL94 standard, and the light transmittance is measured according to the ASTM D1003 standard.

Preparation of intermediate of phosphorus-containing and sulfonic acid group-containing compound represented by formula (IV):

adding 21.62g of DOPO and 20.81g of chloroform into a reaction vessel provided with nitrogen protection, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and mechanical stirring, stirring at room temperature for full dissolution, slowly dropping 12.82g of chlorosulfonic acid and 15g of chloroform mixture into the reaction vessel through the constant pressure dropping funnel at 5 ℃, controlling the reaction temperature to be not more than 60 ℃, after dropping is finished, reacting for 1h at 35 ℃, and finally removing the chloroform and hydrogen chloride through reduced pressure extraction to obtain 35.68g of a compound intermediate containing phosphorus and sulfonic acid groups, wherein the yield is 97%, the weight ratio of DOPO: chlorosulfonic acid: the molar ratio of chloroform is 1:1.1:3.

example 1

Adding 7.41g (about 0.025 mol) of the intermediate compound containing phosphorus and sulfonic acid groups and 30g of ethanol into a reaction vessel provided with a nitrogen protection device, a thermometer, a reflux condenser tube, an isopiestic dropping funnel and a mechanical stirrer, slowly dropwise adding a mixture of 4.62g (4.53 g) (1.

Example 2

Adding 7.41g (about 0.025 mol) of phosphorus-containing and sulfonic acid group-containing compound intermediate and 30g of ethanol into a reaction vessel equipped with a nitrogen protector, a thermometer, a reflux condenser, a constant pressure dropping funnel and a mechanical stirrer, slowly dropping 6.02g (5.91 g) (1. And finally, carrying out reduced pressure filtration, washing the PH of the filter cake by using a mixed solution of water and ethanol to be neutral, and carrying out vacuum drying and grinding to obtain 17.96g of compound powder containing phosphorus, silicon and sulfonate groups, wherein the yield is 98% (theoretically 18.37 g), and the mass content of the S element is 3.9% by using a fluorescence sulfur detector.

Example 3

7.41g (about 0.025 mol) of the intermediate compound containing phosphorus and sulfonic acid groups and 30g of ethanol are added into a reaction vessel equipped with a nitrogen protection device, a thermometer, a reflux condenser tube, an isopiestic dropping funnel and a mechanical stirrer, 4.62g (4.53 g) (1.

Example 4

The procedure of example 1 was repeated except that the mixture of potassium hydroxide and ethanol was replaced with a mixture of sodium hydroxide and ethanol, to give 11.98g (12.49 g) of a solid compound containing phosphorus, silicon and a sulfonate group in a yield of 96%, and the content of S element was 5.1% by mass as measured by a fluorescence sulfur meter.

Example 5

The procedure of example 2 was repeated except that the mixture of potassium hydroxide and ethanol was replaced with a mixture of sodium hydroxide and ethanol, to give 17.58g (17.97 g) of a phosphorus-, silicon-and sulfonate group-containing compound as a solid in a yield of 98%, and the S element content was 3.9% by mass as measured by a fluorescence sulfur meter.

Comparative example 1

5.4g (about 0.025 mol) DOPO and 30g ethanol are added into a reaction vessel which is provided with a nitrogen protection device, a thermometer, a reflux condenser tube, an isopiestic dropping funnel and a mechanical stirrer, 4.62g (4.53 g) (1.02) 1,3-bis (3-glycidyloxypropyl) tetramethyldisiloxane, 10g ethanol and 0.12g Benzoyl Peroxide (BPO) mixture are slowly dropped into the reaction vessel through the isopiestic dropping funnel at the reflux temperature, after 12 hours of reaction is continued after dropping, the solvent and low boiling are removed under reduced pressure, 9.86g (theory 9.93 g) of phosphorus-containing and silicon-containing compound solid is obtained, and the yield is 99%.

Comparative example 2

5.4g (about 0.025 mol) DOPO and 30g ethanol are added into a reaction vessel provided with a nitrogen protection device, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and a mechanical stirrer, 6.02g (5.91 g) (1.02) (3-epoxypropyloxy) propyl trimethoxy silane, 15g ethanol and 0.13g BPO mixture are slowly dropped into the reaction vessel through the constant pressure dropping funnel at the reflux temperature, the reaction is continued for 12 hours after the dropping is finished, after the cooling to the room temperature, 2.7g (0.02mol, 1.34g) methyl trimethoxy silane, 4g (0.02mol, 2.59g) phenyl trimethoxy silane and 0.2g (0.001mol, 0.06g) ethyl orthosilicate mixture are added, a mixed solution of potassium hydroxide and water is added, the pH of the reaction system is adjusted to about 10, the temperature is raised to 60 ℃, a suspended matter is generated after about 1min, and the stirring is continued for 2 hours. And finally, filtering under reduced pressure, washing the filter cake PH by a water and ethanol mixed solution to be neutral, and drying and grinding under vacuum to obtain 12.76g of phosphorus-containing and silicon-containing compound powder with the yield of 93% (theory 13.66 g).

Comparative example 3

18.40g (0.1 mol) of cyanuric chloride was charged into a four-necked flask containing 100mL of acetone, and the temperature of the system was maintained at 0 to 3 ℃ and stirred to be sufficiently dissolved. 13.78g (0.11 mol) of aminoethanesulfonic acid, 6.16g (0.11 mol) of potassium hydroxide were dissolved in 100mL of water, and then added slowly to a solution of cyanuric chloride in acetone. In the reaction process, potassium hydroxide aqueous solution with the concentration of 1mol/L is used for adjusting the pH value of the reaction system, so that the pH value of the system is maintained at 8-9, and the reaction is carried out for 3 hours. After the reaction, the reaction mixture was filtered, and the filter cake was washed with acetone (50 mL. Times.3) and ice water (50 mL. Times.2), and dried at room temperature to obtain TCT-S as a white solid.

Adding 10.83g (0.05 mol) of DOPO into a four-neck flask filled with 50mL of deionized water, heating to 75 ℃, reacting for 4 hours to fully hydrolyze the DOPO, adding 6.00g (0.06 mol) of potassium bicarbonate, adding 1mol/L hydrochloric acid to neutralize to be neutral after the solution is clarified. The solvent was removed by rotary evaporator and dried at 80 ℃ for 6h to give HAPP-K as a white powder.

5.45g (0.02 mol) of HAPP-K was put into a four-necked flask containing 100mL of deionized water, 3.11g (0.01 mol) of TCT-S was dissolved in 100mL of deionized water, and an aqueous solution of TCT-S was slowly dropped into the aqueous solution of HAPP-K using a constant pressure dropping funnel, the temperature of the system was maintained at about 45 ℃ and the pH of the reaction system was adjusted to 9 to 10 by an aqueous solution of KOH at a concentration of 1mol/L during the reaction. When the pH value of the reaction system is not changed any more, the temperature of the system is gradually increased to 90 ℃, and the pH value of the reaction system is adjusted to 9-10 by using KOH aqueous solution with the concentration of 1mol/L in the reaction process. When the temperature of the system is not changed any more, the reaction is stopped, the hot reaction solution is filtered by suction, and the filtrate is concentrated and dried in a vacuum drying oven to obtain light yellow solid. The obtained pale yellow solid was dissolved in anhydrous methanol, insoluble matter was removed by filtration, ethyl acetate of 4 times the volume of the methanol solution was slowly added to the methanol solution while stirring, the mixture was left to stand for 15 minutes, then, suction filtration was carried out under reduced pressure, the cake was washed with ethyl acetate (50 mL. Times.3), and the cake was dried and crushed to obtain 5.90g of NPS-K as a white solid powder.

Comparative example 4

59.5g of phenyltrimethoxysilane, 48.9g of diphenyldimethoxysilane, 58.9g of mercaptopropyltrimethoxysilane, 24g of dimethyldimethoxysilane and 450g of methanol are added into a reaction vessel with a stirring device, a condenser, a thermometer and a dropping funnel, after uniform stirring, the reaction vessel is cooled in a water bath, the internal temperature is kept at 20-30 ℃, 119g of hydrogen peroxide with the content of 30% by mass is dropwise added within 2h, the reaction vessel is stirred at the methanol reflux temperature of 67 ℃ for 5h and then is subjected to ripening reaction, the pH of the reaction system is confirmed to be 1-2 by using a pH test paper when the system is completely white and turbid dispersion liquid, and the residual quantity of hydrogen peroxide is confirmed to be below 0.5 mg/liter by using a hydrogen peroxide detection test paper. Controlling the internal temperature to be 20-50 ℃, adding 72.6g of 30 mass percent potassium hydroxide aqueous solution within 30min, refluxing for 3h at 67 ℃, and testing the pH of the system to be 9 by using pH paper. And (2) evaporating methanol and water in an oil bath at 110 ℃, cooling to room temperature, then adding 500g of methanol, stirring for 1h at room temperature, filtering, putting a filter cake into a mixed solvent consisting of 200g of methanol and 300g of water, dispersing under the cooling condition of ice water, filtering, washing with acetone, drying under reduced pressure, and grinding to obtain 128g of silicon-containing and sulfonate-containing compound powder.

Example 6

5g of each of the samples of examples 1,2,3,4 and 5 was put in water at room temperature and 100 ℃ and stirred for 1 minute, and almost no dissolution occurred. 5g of potassium 3-benzenesulfonyl benzenesulfonate (KSS) and potassium perfluorobutylsulfonate (FR-2025) which are widely used in the market were put into water at room temperature and 100 ℃ respectively, and stirred for 1 minute to be dissolved completely.

5g of each of the samples of comparative example 1,2 was placed in water at room temperature and 100 ℃ and stirred for 1 minute until almost no dissolution occurred.

5g of the samples of the comparative examples 3,4 in the background art were put in water at room temperature and 100 ℃ respectively, and stirred for 1 minute, so that the comparative example 3 was completely dissolved, and the comparative example 4 was almost not dissolved.

Therefore, compared with KSS and FR-2025 flame retardants widely used in the market and the phosphorus-containing, nitrogen-containing and sulfonate compound in the comparative technology in comparative example 3, the phosphorus-containing, silicon-containing and sulfonate compound provided by the invention has better water solubility resistance.

Examples 7 to 11 and comparative examples 5 to 9

The phosphorus-containing, silicon-containing and sulfonate compounds prepared in examples 1-6 of the invention and the compounds prepared in comparative examples 1-4 are used as flame retardants, and then compared with common flame retardants and flame-retardant substrates for performance detection.

Mixing the corresponding components by a mixer, confirming the uniform mixing, extruding and granulating by using a double-screw extruder, injecting the obtained granules into a required standard sample strip by an injection molding machine, and finally carrying out relevant standard tests. The PC was dried at 120 ℃ for 4h before use. The length-diameter ratio of the used double-screw extruder is 40, the double-screw extruder is provided with accurate temperature control and vacuum exhaust equipment, the rotating speed of the screw is 100-700 r/min, and the extrusion working temperature is as follows: the first zone is 230-260 ℃, the second zone is 230-270 ℃, the third zone is 230-270 ℃, the fourth zone is 240-280 ℃, and the retention time is 1-2 minutes. The light transmittance (molded 80mm 40mm 3.2mm thick plaques, according to ASTM D1003), flame retardant properties and flame retardant properties of the polymer composition plaques after boiling water treatment for 1 hour were characterized.

Referring to Table 1, table 1 shows the formulations and performance data for the polymer compositions prepared in examples 7-11 of the present invention and comparative examples 5-9.

TABLE 1

In which Polycarbonate (PC) (from SABIC) and the phosphorus-, silicon-and sulfonate-containing compounds, KSS, phosphorus-and silicon-containing compounds of the present invention, the phosphorus-, nitrogen-and sulfonate-containing compounds of the comparative examples, and the polymer compositions containing the silicon-and sulfonate-containing compounds were prepared as shown in Table 1 in examples 7 to 11 and comparative examples 5 to 9.

According to the test results in table 1, the flame retardant containing phosphorus, silicon and sulfonate compounds of the present invention can prepare a flame retardant V0 suitable for transparent PC or natural color non-transparent PC according to the difference of the structures of the introduced silicon compounds, such as PC with flame retardant of the product of example 1,3,4 has higher light transmittance, and the product of example 2 is more suitable for flame retardant of natural color non-transparent PC. Due to the synergistic flame retardant effect of phosphorus, silicon and sulfonate, the product of the invention has better flame retardant effect under the condition of the same addition amount, and due to the introduction of different silicon compound structures, the prepared flame retardant polymer composition has better water precipitation resistance and flame retardant durability.

The foregoing detailed description of a phosphorus, silicon and sulfonate containing compound of the present invention, and the preparation and use thereof in the polymer processing field, has been presented in terms of specific examples to illustrate the principles and practice of the invention, and the description of the examples is provided to facilitate an understanding of the process and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated processes. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

1. A compound containing phosphorus, silicon and sulfonate is characterized by having a general formula shown in a formula (I);

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

said M comprises a metal and/or, ammonia/amine compound;

the R is ⁴ 、R ⁵ Each independently selected from one or more of halogen, nitro, C1-C15 alkyl and C1-C15 alkoxy。

2. The compound of claim 1, wherein the compound comprises a flame retardant;

the compound is a solid;

the mass percentage of the S element in the compound is 0.001-30%;

3. A compound of claim 1, wherein R is ⁴ And R ⁵ Can form a saturated or unsaturated cyclic ring;

in the formula (I), R ³ _f SiO _(4-f)/2 The mol content of the chain link is 0mol% -90 mol%;

in the formula (I), siO ₂ The molar content of the chain link is 0mol% -90 mol%;

and b is 1.

4. A method for preparing a compound containing phosphorus, silicon and sulfonate is characterized by comprising the following steps:

2) Carrying out addition reaction on the compound containing phosphorus and sulfonic acid groups obtained in the step and a silicon compound containing epoxy groups, and then carrying out neutralization or precipitation reaction on the compound containing phosphorus and sulfonic acid groups and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, silicon and sulfonic acid with a structure shown in a formula (I);

or:

2') carrying out neutralization or precipitation reaction on the compound containing phosphorus and sulfonic acid groups obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the compound and a silicon compound containing epoxy groups to obtain a compound containing phosphorus, silicon and sulfonic acid salts with a structure shown in a formula (I);

or:

2'), carrying out sulfonation reaction on the intermediate of the compound containing phosphorus and silicon obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate of the compound containing phosphorus and silicon and the compound containing metal and/or ammonia/amine to obtain a compound containing phosphorus, silicon and sulfonate with a structure shown in a formula (I);

(R ¹ _a R ² _g SiO _(4-a-g)/2 ) _n (R ³ _f SiO _(4-f)/2 ) _q (SiO ₂ ) _m

(I)；

f is an integer, and f is more than or equal to 3 and more than or equal to 1;

said M comprises a metal and/or, ammonia/amine compound;

5. The method of claim 4, wherein the sulfonating agent comprises one or more of concentrated sulfuric acid, oleum, chlorosulfonic acid, and sulfur trioxide;

the temperature of the sulfonation reaction is 0-150 ℃;

the sulfonation reaction time is 0.5-10 h.

6. The production method according to claim 4, wherein the silicon compound containing an epoxy group comprises one or more of a silicon compound represented by the formula (VI), a hydrolysate thereof, and a partial hydrolysis-condensate thereof:

R ⁶ _a R ² _g SiX _(4-a-g) (Ⅵ)；

each X is independently bonded to a silicon atom;

said X comprises a halogen and/or a hydrolysable group;

the R is ⁶ Is an organic group containing an epoxy group;

each of said R ⁶ Independently of one another, to the Si atom;

7. The method of claim 6, wherein R is ⁶ Comprises 3- [ (2,3) -glycidoxy]One or more of propyl, 2- (3,4-epoxycyclohexyl) ethyl, and (3-glycidyl) propoxy-substituted heptaisobutyl;

the temperature of the addition reaction is 50-160 ℃;

the time of the addition reaction is 2-20 h;

8. The production method according to claim 4, wherein the metal compound comprises a metal compound that ionizes a metal ion in a solvent;

the metal compound comprises one or more of an alkali metal compound, an alkaline earth metal compound, aluminum sulfate and aluminum nitrate;

9. A flame retardant polymer composition comprising the phosphorus, silicon and sulfonate containing compound according to any one of claims 1 to 3 or the phosphorus, silicon and sulfonate containing compound prepared by the preparation method according to any one of claims 4 to 8.

10. The flame retardant polymer composition of claim 9 wherein the polymer matrix of the flame retardant polymer composition comprises one or more of polycarbonate, epoxy resin, polyphenylene ether, polyalkylene terephthalate, vinyl polymer, polyalkylene, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and silicone rubber;

additives are also included in the polymer composition;