KR20010082738A - Polyorganosilsesquioxane and process for preparing the same - Google Patents

Abstract

PURPOSE: Polyorganosilsesquioxanes, their precursor, and their preparation method are provided, to improve the crystallinity of laddered structure, thereby to improve the heat stability, the gap filling capability and the adhesion and to reduce the permittivity, the absorptivity and the thermal expansion coefficient. CONSTITUTION: The polyorganosilsesquioxanes are represented by the formula 1. The precursor for preparing the compound of the formula 1 is 1,3-diorganosiloxane represented by the formula 2. In the formulas 1 and 2, R1 and R2 are independent each other and are H, a substituted or unsubstituted aliphatic hydrocarbon group of C1-C30, a substituted or unsubstituted aromatic hydrocarbon group of C1-C30, a substituted or unsubstituted cyclic hydrocarbon group of C1-C30, a substituted or unsubstituted silyl group of C1-C30, a substituted or unsubstituted allyl group of C1-C30, a substituted or unsubstituted acyl group of C1-C30, a vinyl group, an amine group, an acetate group or an alkali metal; R3 are H, an alkyl group of low molecular weight, an acetate group, Na or K; X is H, a halogen atom, a hydroxy group, an amine group or a carboxyl group; and n is an integer of 2-300,000. The polyorganosilsesquioxanes of the formula 1 is prepared by polycondensation of the compound of the formula 2 in an organic solvent (See reaction scheme).

Description

Polyorganosilsesquioxane and its manufacturing method {Polyorganosilsesquioxane and process for preparing the same}

The present invention relates to a polyorganosilsesquioxane and a method for producing the same, and more particularly, to a polyorganosilsesquioxane having a silane compound as a starting material and a method for producing the same.

Recently, with the development of advanced technology field, the development of high-performance multifunctional high-tech materials has been studied in various fields. In particular, the research on new polymer materials is a new technology that is attracting the most attention for the formation of organic or inorganic hybrids such as complexes having a mixed structure of organic and inorganic materials with high functionalization of organic polymers such as improvement of heat resistance or glass transition temperature (Tg). It is attracting attention.

There are a variety of organic or inorganic hybrid materials known in the art, but the thermal stability between the organic polymer and the inorganic polymer is particularly important, so the most attention among them is polyorganosilsesquioxane, which is a high heat resistant polymer. Can be.

Polyorganosilsesquioxanes have been synthesized by Owens Illinois and Gelest since they were first synthesized in Brown et al. (J.Am. Chem . Soc ., 82, 6194 (1960)). It was commercialized under the name of “Glass-Resin” and “SST-Resin”, but the difficulty of controlling the polymer structure and controlling the molecular weight makes it difficult for high molecular weight to be applied. However, because the improved properties of polyorganosilsesquioxanes are due to the highly regular ladder form structure, condensation with the development of new starting materials that are easy to form a ladder structure Research into the method has been conducted in various ways in various fields.

Representative methods of preparing polyorganosilsesquioxane known to date are low molecular weight polymers (Mn of 20,000 to 20,000) by dehydrating and condensing precursor hydrolyzate (oligomer) obtained by hydrolyzing trichlorosilane or trialkoxysilane under an alkali / acid catalyst. About 30,000, and its molecular weight distribution (Mn / Mw) of about 3 to 5) can be easily prepared. First, a conventional method of preparing polyorganosilsesquioxane using trichlorosilane will be described. do. When hydrolyzing trichlorosilane, the condensation reaction proceeds simultaneously with the hydrolysis, and the oligomer (Mn is 1,000 to 2,000 and PDI is 2 to 5) is not a single structure of silanetriol, but it is complex. It has a variety of structures, it is easy to form a three-dimensional network structure due to the inter-hydroxyl group and random self-structure of the oligomer caused by the presence of a hydroxyl group in the molecule in the case of high molecular weight using it Therefore, it has been found to have the following disadvantages. That is, 1) it is impossible to control the structure of the produced polymer, 2) it is difficult to control the molecular weight of the produced polymer and to obtain a high molecular weight polymer, and thus 3) the produced polymer loses its regularity, thereby reducing its solubility in solvents, 4) Particularly, the remaining low molecular weight component has a problem of adversely affecting the heat resistance and mechanical properties of the polymer.

In addition, the conventional method of preparing polyorganosilsesquioxane using trialkoxysilane also has advantages in that it is easier to handle such as hydrolysis reaction rate control than the trichlorosilane. Molecular defects of oligomers caused by the presence of hydroxy groups and the presence of alkoxy groups have the following disadvantages.

That is, 1) a branched polymer, not a ladder structure, is produced, and 2) the selection and amount of catalyst used, the choice of reaction solvent, and the precise pH control of the reaction solution are necessary, but the adjustment is not easy. There is an unsuitable problem in manufacturing a highly regular silicon ladder-type polymer, such as forming a three-dimensional network structure to form a microgel to some extent.

As described above, the interest in polyorganosilsesquioxane has been extensively studied since the past, but various synthetic methods known to date, such as sol-gel method, ring-opening polymerization method, equilibrium polymerization method, etc. And the condensation process is known to be very complicated through various structural studies, so that the commercially available products such as trade name glass resin, so-called tee-type resin, etc. may also be used as new industrial materials. Due to the problem of not being able to meet various conditions, there is a certain limit to practical use. Currently, the conditions to be used as an industrial new material element using organic or inorganic hybrid materials are low dielectric constants of about 2 to 3 and a thermal decomposition start temperature of 400. Excellent thermal stability above ℃, low hygroscopicity, low That having a coefficient of expansion, good gap filling capability (gap filling capability), and properties such as good adhesion is preferable.

In order to solve the above-mentioned problems, the inventors used a high-purity organosilanetriol instead of oligomers having various molecular weights and structures, and thus the regularity of the structure could not be controlled by conventional synthetic methods. / Crystalline polyphenylsilsesquioxane was synthesized.

However, there remains a need for polyorganosilsesquioxanes with better high regularity / crystallinity.

The technical problem to be achieved by the present invention is 1) easy to handle, 2) easy to control the polymerization rate, 3) the hydroxy group is uniformly present in the polymer sock end, 4) high-regular R- SiO _3/2 can be introduced, and 5) the structure of polymer crosslinking, in particular, the degree of crosslinking, crosslinking density, etc. can be easily controlled, and 6) chemical reaction for promoting a chemical reaction by unfolding the structure of the polymer. It can facilitate nitriding, 7) the formation of pores at the nanoscale or molecular level in the size of the dispersed phase in the polymer skeleton, 8) the development and manufacturing method of a new precursor that can impart high functionality and various properties to the polymer A new high-tech inorganic polymer having excellent properties by the development of.

In the present invention, it is an object of the present invention to provide a polyorganosilsesquioxane and a method for producing the same for achieving the above technical problem.

The polyorganosilsesquioxane provided by the present invention to solve the object of the present invention is a compound of formula (1).

Wherein R ₁ and R ₂ are independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted 1 to 30 carbon atoms Or an unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms , Vinyl group, amine group, acetate or alkali metal, n represents an integer of 2 to 300,000.)

In the present invention, as a precursor for preparing the polyorganosilsesquioxane of Chemical Formula 1, 1,3-diorganosiloxane is provided.

(Wherein R ₁ and R ₂ are as defined above, R ₃ represents hydrogen, lower alkyl group, acetate, sodium or potassium, and X represents hydrogen, halogen, hydroxy group, amine group or carboxyl group.)

The preparation method for preparing the polyorganosilsesquioxane of the present invention is shown in Scheme 1 below.

Wherein R ₁ , R ₂ , R ₃ , n and X are as defined above.

Step (A) of Scheme 1 is a process for preparing the compound of Formula 2, which is a precursor for preparing the compound of Formula 1, which is the polyorganosilsesquioxane of the present invention. Various kinds of compounds of formula (2) can be easily synthesized by reacting under an acidic or non-catalyst using compounds of formula (3) such as compound of formula (4) and trimethoxyphenylsilane.

The organic solvent used in the reaction is not particularly limited as long as it is a conventionally used organic solvent, but THF, benzene, anosol, chlorobenzene, xylene, MIBK, DMF, NMP, 1,4-dioxane, DMAc, acetone or toluene Etc. are preferable.

The catalyst used in the reaction is preferably HCl, acetone, triethylamine, tin, pyridine, trichloroacetic acid or acetic acid-amine complex catalyst and the like, but trichloroacetic acid is particularly preferable in terms of reaction rate, reaction temperature and yield.

The reaction temperature of the reaction is preferably 30 to 350 ° C, and the reaction time is preferably 1 to 300 hours.

Polyorganosilses of the formula (1) by polycondensing the compound of the formula (2) obtained as a precursor in a conventional manner in a conventional manner using the compound of formula (2) obtained as described above in the step (B) of Scheme 1 Quioxane can be obtained.

The polycondensation method of step (B) of Scheme 1 is not particularly limited, but various methods such as heating, light irradiation, electron beam injection, or microwave irradiation can be used, and when a catalyst is further used, a compound having a large n value can be obtained. It is possible.

The compound of Formula 2 used in the step (B) of Scheme 1 is preferably used in the range of 5 to 300 parts by weight, preferably 10 to 100 parts by weight based on 100 parts by weight of the organic solvent. If the amount of the compound of Formula 2 is less than 5 parts by weight, the polycondensation reaction is late or the reaction does not proceed sufficiently. If it exceeds 300 parts by weight, gelation may occur during the reaction, which is not preferable.

The catalyst used to promote the polycondensation reaction of step (B) of Scheme 1 in principle is not limited, but preferably alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene tri It is preferable to use at least one substance of amines such as amine, meta-butylamine, para-dimethylamine ethanol, triethanolamine, or quaternary ammonium salts or fluorides. The catalyst for the condensation reaction is preferably used in the range of 0.001 to 5 parts by weight, preferably 0.001 to 1 part by weight based on 100 parts by weight of the compound of Formula 2.

In particular, in the case of using the alkali metal hydroxide in the catalyst as a catalyst, it is more preferable to produce a hydrolyzate by hydrolyzing the compound of Formula 2 in advance, and then proceed with the polycondensation reaction.

The organic solvent used in the reaction of Scheme 2 is not particularly limited, but an organic solvent having a boiling point of 100 ° C. or higher, for example, toluene, NMP, or the like is preferably used.

The reaction temperature of the polycondensation reaction used in the step (B) of Scheme 2 is in the range of 50 to 350 ℃, it is preferable to react at 100 to 150 ℃, wherein the reaction time is 1 when using a catalyst It is preferable to adjust in the range of -50 hours, and when not using a catalyst, it is preferable to make it react for 1 to 200 hours in the range of 150-350 degreeC. If the polycondensation temperature is lower than or exceeded, there is a problem that the efficiency of the condensation reaction is not made to an industrial degree.

In addition, when the purity of the compound of Chemical Formula 2 for the polycondensation reaction is 90% or more, a high molecular weight polymer (Mn> 500,000) may be obtained by different manipulation methods.

The polyorganosilsesquioxane represented by Chemical Formula 1 provided in the present invention has high solubility in general organic solvents, and aromatic hydrocarbons such as toluene, xylene, benzene, chlorobenzene, methylene chloride, chloroethane, and the like. It is soluble in hydrocarbons, ethers such as THF, 1,4-dioxane, diethyl ether and dibutyl ether, ketones such as acetone, methyl ethyl ketone and methyl ether ketone, esters and organic solvents such as dimethylformamide.

As used herein, the terms R ₁ and R ₂ are independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or 1 carbon atom. Substituted or unsubstituted alicyclic hydrocarbon group of 30 to 30, substituted or unsubstituted silyl group of 1 to 30 carbon atoms, substituted or unsubstituted allyl group of 1 to 30 carbon atoms, substituted or unsubstituted 1 to 30 carbon atoms A substituted acyl group, vinyl group, amine group, acetate or alkali metal, preferably lower alkyl group such as hydrogen, methyl group, ethyl group or propyl group, phenyl group, phenol group, chlorophenyl group, vinyl group, carboxyl group, trimethylsilyl group , Acetate, alkali metal and the like, and more preferably hydrogen, methyl group, phenyl group, vinyl group, trimethylsilyl group and the like.

Example

Hereinafter, the present invention will be described in detail with reference to examples, and detailed description will be made with reference to the accompanying drawings in order to help understanding of the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1 Preparation of Compound (1,1-Dichloromethyl-3,3-diethoxyphenylsiloxane) of Formula 2 (R _One = Methyl, R ₂ = Phenyl)

A three-neck 500 ml round bottom flask was equipped with a reflux condenser and a 100 ml dropping funnel, and then flame dried in a nitrogen atmosphere. 19.8 ml of trimethoxyphenylsilane and 1.6 ml of CCl ₃ COOH were dissolved in 380 ml of acetone and stirred for 4 hours. After 4 hours, 15 ml of trichloromethylsilane was slowly added dropwise through a dropping funnel, followed by 72 hours of reaction at room temperature. After the reaction, a vacuum distillation unit was installed in the reactor, and unreacted trimethoxyphenylsilane, trichloromethylsilane and CCl ₃ COOH were distilled off to obtain a white transparent solution. (Yield 86%)

¹ H NMR (500 MHz / CDCl ₃ ): δ 0.2 (s, Si-Me), 3.5 (s, Si-OMe),

7.2 to 7.8 (d, Si-Ph) ppm

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ-7.5 (s, Si-OCH ₃ ),-24.8 (s, Si-Cl) ppm

GC / Mass: Mn = 296

Example 2: Hydrolysis of the Compound of Formula 2 (1,1-Dichloromethyl-3,3-diethoxyphenylsiloxane)

A three-neck 500 ml round bottom flask was equipped with a reflux condenser and a 100 ml dropping funnel, and then flame dried in a nitrogen atmosphere. 30 ml of the compound (1,1-dichloromethyl-3,3-diethoxyphenylsiloxane) obtained in Example 1 was dissolved in 70 ml of toluene and then transferred to a dropping funnel. 350 ml of tertiary distilled water and HCl were added to a 500 ml round bottom flask to pH 2.5, and 1,1-dichloromethyl-3,3-diethoxyphenylsiloxane was slowly added dropwise through a dropping funnel and hydrolyzed at 3 ° C. After the hydrolysis reaction, the organic layer and the aqueous layer were separated with a separatory funnel, and the aqueous layer was recrystallized at 3 ° C. to obtain a white transparent powder of Ph (OH) ₂ SiOSiMe (OH) _{2 as} a hydrolyzate. (Yield 88%)

The white powder was dried at low temperature at 3 ° C. and used as analytical sample.

¹ H NMR (500 MHz / CDCl ₃ ): δ 0.8 (s, Si-Me), 2.7-3.25 (s, Si-OH),

7.3 to 7.78 (d, Si-Ph) ppm; Si-Me / Si-OH / Si-Ph = 25.77 / 23.18 / 16.36 = 3/4/5

LC / Mass: Mn = 295.9

Example 3: Hydrolysate (Ph (OH)) ₂ SiOSiMe (OH) ₂ ) Polycondensation

The Dean-Stark tube was placed in a 50 ml round bottom flask and flame dried in a nitrogen atmosphere. 10 g of the hydrolyzate Ph (OH) ₂ SiOSiMe (OH) ₂ and 0.1 g of potassium hydroxide obtained in Example 2 were placed in a flask, and 38 ml of toluene was added to dissolve Ph (OH) ₂ SiOSiMe (OH) ₂ . Subsequently, the reaction was carried out at a reflux temperature of toluene for 18 hours. After the reaction, the mixture was added dropwise to methanol, stirred for 30 minutes, and the resulting precipitate was filtered to give a reaction product (yield: 98%) as a white powder. The product was vacuum dried at 50 ° C. for 10 hours and used as analytical sample.

¹ H NMR (500 MHz / CDCl ₃ ): δ -0.5 to 0.8 (s, Si-Me), 7.11 to 7.8 (s, Si-Ph) ppm

IR (KBr): 3080-2940 (CH), 1435 (Si-Ph), 1050 (O-Si-Ph), 1150 (O-Si), 750,700 (Ph) cm ^-1

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -67.7 (Me-T ₃ ), -83.7 (Ph-T ₃ ) ppm

GPC (Pst); Mn = 35,244

Td = 480 ℃

Degree of crosslinking (DC); DC (%) = T ₃ / T _total 100 = 98%

Low k = 2.72

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention and are not intended to limit the scope of the present invention as defined in the meaning or claims.

According to the present invention described above, unlike the polyorganosilsesquioxane obtained by heat condensation of an oligomer obtained by hydrolyzing trichlorosilane or triethoxysilane, a silane-based compound is first reacted with a starting material, 1,3. Since polyorganosiloxane is obtained by polycondensation of diorganosiloxane to obtain polyorganosilsesquioxane, a highly regular ladder polymer having a structural feature of cyclic tetraorganosilsesquioxane, which is a repeating unit structure, can be synthesized.

In this way, since the siloxane bond (Si-O-Si) and the ladder structure can be easily formed in the polymer backbone, high heat resistance can be maintained, and the existence ratio of hydroxy groups to each other or to the defect structure can be reduced. This eliminates the need for heat treatment and allows the introduction of a variety of functional side chains (photosensitive groups, dealkylated reactive groups, etc.), especially changes in the physical properties of polymers and new properties depending on the composition of introduced side chain ratios (e.g. The molecular design of the polymer can be made possible, and the silanol end groups can be uniformly arranged at the end of the polymer, so that the introduction amount of the organic polymer of the organic or inorganic hybrid production can be controlled to easily prepare the organic or inorganic copolymer. Has the advantage.

In particular, the polyorganosilsesquioxane prepared according to the method provided by the present invention has a siloxane bond (Si-O-Si) and a rigid ladder structure (R-O-Si) in the main chain than the polyorganosilsesquioxane prepared by the conventional method. -SiO _3/2 ) contains 97% or more (number of R-SiO _3/2 ÷ (number of hydroxyl groups + silanol terminal groups) x 100) so that it has a solubility in general organic solvents It exhibits high heat resistance (temperature of pyrolysis starting above 500 ° C), weather resistance, low surface tension, optical transparency, low dielectric constant (3.0 or less), low absorption rate, excellent gap filling capability, and the like. In addition, different side chains have excellent properties such as adhesion to metals such as aluminum, copper, titanium, silicon, and glass, electrical insulation, drainage, chemical resistance, transparency, etc. Commercial applications are possible. UV curing resins and silane compounds are widely used in the polyorganosilsesquioxane prepared by the present invention, but glass resins are widely used in some cases. Examples of the material include polycarbonate, acrylic resin, diethyl glycol bisalkyl carbonate (trade name "CR-39"), and the use thereof includes plastics, sunglasses, safety glasses, dashboards, automobile lamps, aircraft window glass, bulletproof glass, and the like. Can be used. It may also be used for the purpose of heat-treating the spectacle lens with glass resin.

In addition, the polyorganosilsesquioxane obtained according to the present invention is excellent in electrical insulation, heat resistance, low water absorption, flattening effect of spin-on glass (SOG) solution, and is suitable for use in electronic relations. For example, a protective coating film of a thin film, an interlayer insulating film of an LSI multi-impedance wiring, and a low dielectric material may be used as a low dielectric material, a multilayer insulating film, a liquid crystal display insulating film, and the like.

On the other hand, in recent years, since the spacing between wirings is considerably narrowed, highly integrated semiconductor devices have inevitably become thick and have a problem that cracks occur. Such cracking phenomena include 1) thermosetting shrinkage stresses generated by condensation between hydroxy and inter-hydroxy groups or terminal-silanol groups, 2) cured film and aluminum wiring, It is known to be due to the difference in thermal stress due to the difference in the coefficient of thermal expansion with the silicon wafer, the present invention is low in the presence of hydroxy group (inter-hydroxy) due to the defect structure in the polymer structure (5 % Or less), silanol ends, silicides, double bonds, etc., to block reactions occurring at the ends and at the same time other organic polymer materials, in particular polyimide, polyamide, PMMA, polyacryl, By introducing polycarbonate, polystyrene, polyurethane, etc., it is possible to impart new functionality of organic-inorganic hybrid and solve the conventional problems. Have. In addition, since the polyorganosilsesquioxane prepared according to the present invention is dissolved in various solvents to form a thin film easily, has a high hardness (4 to 8H) for thermosetting, and a thin film having good transparency can be formed, The long-term reliability of optical fiber can be improved by commercializing with photofunctional organic polymer. Moreover, since it can use as a material which forms a coating layer on the surface of a resistor, it can be applied also to an electrical / electronic material.

And when molding plastic such as urethane RIM (Reactive Injection Molding), it can be used as a metal release agent. It can also be used as a release agent in the manufacture of glass bottles. In addition, the polyorganosilsesquioxane provided in the present invention can be mixed with RTV and used as a tile adhesive for a space shuttle, and can also be used as a binding agent for an optical fiber, and features such as outer coating and heat resistance and corrosion resistance of a space shuttle. It can also be used for heat-resistant paints.

End products provided by the present invention listed above will continue to be expanded with the development of the state of the art, so that the scope of application is not limited to the above uses, the expansion of the use will be infinite.

Claims (11)

A compound of formula 1 Wherein R ₁ and R ₂ are independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted 1 to 30 carbon atoms Or an unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms , Vinyl group, amine group, acetate or alkali metal, n is an integer of 2 to 300,000.) The compound of formula 1 according to claim 1, wherein R ₁ and R ₂ independently represent hydrogen, methyl group, phenyl group, vinyl group or trimethylsilyl group, and n is an integer of 1,000 to 100,000. A compound of formula Wherein R ₁ and R ₂ are independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted 1 to 30 carbon atoms Or an unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms Represents a vinyl group, an amine group, an acetate or an alkali metal, R ₃ represents hydrogen, a lower alkyl group, acetate, sodium or potassium, and X represents hydrogen, a halogen, a hydroxy group, an amine group or a carboxyl group.) 4. A compound according to claim 3, wherein R ₁ and R ₂ independently represent hydrogen, methyl group, phenyl group, vinyl group, trimethylsilyl group, R ₃ represents hydrogen, methyl, acetate, sodium or potassium, and X represents hydrogen, chlorine, hydroxide A compound of formula (2) characterized by representing a hydroxy, amine or carboxyl group. A process for producing a compound of formula 1 below, which is obtained by polycondensation reaction of a solution of a compound of formula 2 in an organic solvent. Wherein R ₁ and R ₂ are independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted 1 to 30 carbon atoms Or an unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms , A vinyl group, an amine group, an acetate or an alkali metal, R ₃ represents hydrogen, a lower alkyl group, acetate, sodium or potassium, X represents a hydrogen, a halogen, a hydroxy group, an amine group or a carboxyl group, n is 2 to 300,000 Represents an integer.) The production method according to claim 5, wherein the polycondensation reaction is any one selected from the group consisting of heating reaction, light irradiation reaction, microwave irradiation reaction or electron beam irradiation reaction. The method according to claim 5, wherein the amount of the compound of Formula 2 is 5 to 300 parts by weight based on 100 parts by weight of the organic solvent. The process according to claim 5, wherein the process is further carried out in the presence of a polycondensation catalyst. The polycondensation reaction catalyst according to claim 8, wherein the polycondensation reaction catalyst is sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene triamine, meta-butylamine, para-dimethylamine ethanol, triethanolamine, quaternary ammonium salts, or fluorine. At least one substance selected from the group consisting of cargoes. The method according to claim 8, wherein the polycondensation reaction catalyst is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the compound of Formula 4. A method for preparing a compound of Formula 2, comprising reacting a compound of Formula 3 and Formula 4 to produce a compound of Formula 2. (Wherein R ₁ , R ₂ , R ₃ and X are as defined in claim 1 or 2).