WO2007037642A1

WO2007037642A1 - Process for the modified polymers by the modification of chlorine containing polymers

Info

Publication number: WO2007037642A1
Application number: PCT/KR2006/003910
Authority: WO
Inventors: Jong-Hoon Kim
Original assignee: Hae Dong Chemical Co., Ltd.
Priority date: 2005-09-29
Filing date: 2006-09-29
Publication date: 2007-04-05

Abstract

The present invention relates to a method for preparing novel modified polymers by substituting the chlorine of chlorine-containing polymers. The modified polymers prepared by the method can be used in a mixture with various plastics to increase antistatic properties, adhesive properties, antioxidant properties, and ink adhesion and thus printability upon ink printing or coating, in formed articles, fibers, films or sheets. The invention comprises substituting 1-99.9 mol% of the chlorine atoms of chlorine-containing polymers with substituents.

Description

[DESCRIPTION]

[invention Title]

PROCESS FOR THE MODIFICATION OF

CHLORINE-COTAINING POLYMERS VIA

AMINATION REACTION

[Technical Field]

The present invention relates to a method for preparing novel modified polymers by substituting the chlorine of chlorine-containing polymers. The modified polymers prepared according to the inventive method can be used in a mixture with various plastics to increase antistatic properties, adhesive properties) antioxidant properties, and ink adhesion and thus printability upon ink printing or coating, in formed articles, fibers, films or sheets.

[Background Art] Till now, chlorinated polypropylene or chlorinated polyethylene has been used to improve the adhesive properties of polypropylene or polyethylene, and polyvinyl chloride and the like have been used in specific applications, but an example of the use thereof after substituting the chlorine thereof could not yet be seen. Methods of modifying these chlorine-containing polymers through substitution reactions are disclosed in, for example, Korean Patent Application No. 10-2004-00117574, entitled "modified polymers resulting from amine modification of chlorinated polypropylene and preparation method thereof", Korean Patent Application No. 10- 2005-0001443, entitled "surface-modified polymers of blend of polypropylene and chlorinated polypropylene and preparation method thereof", Korean Patent Application No. 10-2005-0037289, entitled "amine-modified polymers of chlorinated polyethylene and preparation method thereof", and Korean Patent Application No. 10-2005-0037650, entitled "amine-modified polymers of polyvinyl chloride or polyvinyl chloride copolymer and preparation method thereof", which were developed by the present inventors. Also, polyamines, cationic polymer coagulants, which have been used in water treatment, paper-making and adhesive applications, have good performance, but are expensive because the cost of monomers thereof is high or preparation methods thereof are complicated. Thus, these polymer coagulants do not have the ability to compete with inorganic coagulants in the market. Accordingly, there is an increasing need for a novel polymer composition capable of cost-effectively substituting for polyamines, which have been used in water treatment, papermaking, adhesive applications, etc.

[Disclosure]

[Technical Problem]

The present inventors have conducted various studies to solve the above-described problems occurring in the prior art and, as a result, found methods capable of preparing various modified polymers by substituting the chlorine of chlorine- containing polymers with various substituents .

Accordingly, it is an object of the present invention to provide a novel method of preparing novel modified polymers by substituting the chlorine of chlorine-containing polymers. Another object of the present invention is to provide a method of preparing novel modified chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride or polyvinyl chloride copolymer.

Still another object of the present invention is to provide novel modified chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride or polyvinyl chloride copolymer, which can be used in combination with various plastics to increase antistatic properties, adhesive properties, antioxidant properties, and ink adhesion and thus printability upon ink printing or coating, in formed articles, fibers, films or sheets.

Yet still another object of the present invention is to provide novel modified chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride or polyvinyl chloride copolymer, which can be prepared inexpensively and made into cationic polymer aqueous solutions capable for substituting for expensive polyamine aqueous solutions, which have been used in water treatment, papermaking, adhesive applications, etc. [Technical Solution] To achieve the above objects, the present invention provides a method for preparing a modified polymer, which comprises the steps of: 1) dissolving a - chlorine-containing polymer in a solvent; 2) mixing the solution with a chlorine- substituting substance and a reaction-promoting substance capable of removing byproduct hydrochloric acid; 3) heating the mixture to allow it to react; 4) removing unreacted material and salts after the reaction, 5) removing the solvent to recover the modified polymer. As used herein, the term "chlorine-containing polymers" refers to polymers containing chlorine in the molecule, such as chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride, or polyvinyl chloride copolymer, but the present invention is not limited thereto. In step 1) , the solvent is not specifically limited as long as it can dissolve all the chlorine-containing polymers, the chlorine-substituting substance and the modified polymers obtained after the reaction. The chlorine-substituting substance itself can also be used as the solvent, and the chlorine-substituting substance itself can also promote the reaction by trapping byproduct hydrochloric acid. The choice of the solvent can be varied depending on the kind of resin to be modified, and examples of solvents, which can be used in the present invention, include toluene, xylene, ethylbenzene, acetonitrile, alkyleneglycol dialkylether, tetrahydrofuran, dioxane, morpholine, N-alkyl morpholine, and mixtures of two or more thereof, but are not limited thereto. Particularly, it was found that, if morpholine or N-alkyl morpholine was used alone or in a mixture with other solvents in a reaction for substituting polyvinyl chloride, modified polymers could be prepared which had a very high chlorine substitution of amine, which was distinguishable from the use of other solvents, even though the reason therefor could not been understood. In this case, morpholine can participate in the reaction to some extent according to conditions.

In step 2), the chlorine-substituting substance can be exemplified by amine, ammonia, metal hydroxide or the like. When a substituting substance having low boiling point is used, a process of making the substituting substance into a liquid phase using a high-pressure reactor is used. The metal hydroxide may be at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Also, when metal oxide was added during the procedure of the reaction, a modified polymer having a good color could be unexpectedly prepared. This is thought to be because the metal oxide can remove water to reduce elimination reactions of hydrochloric acid from a polymer, thus making a product having a good color. The metal oxide is not specifically limited as long as it can remove water, but is generally one or more selected from the group consisting of magnesium oxide, calcium oxide, strontium oxide, and barium oxide.

Also, when an antioxidant is added into the reaction system during the chlorine substitution reaction of the present invention, it can maximize the effect of reducing elimination reactions from a polymer to make a product having a good color. The antioxidant may be a general-purpose product, which is generally used in polymer substances, and examples thereof include 1, 1, 3-tris- (2-methyl-4-hydroxy-5-tert- butylphenyl) butane (Chemische Werke Lowi, Lowinox CA 22) and the like, but are not limited thereto.

To promote the chlorine substitution reaction, a reaction-promoting substance can be used which serves to remove byproduct hydrochloric acid resulting from the reaction between chlorine ions produced from chlorine-substituted polymers by substitution and the hydrogen ions of the chlorine-substituting substance. Examples of the reaction- promoting substance capable of removing hydrochloric acid during the reaction in the present invention include amines such as triethylamine, trimethylamine, triethylenediamine, N- alkyl morpholine, and morpholine, metal hydroxide, metal carbonate, metal oxide and metal carboxylate. The reaction- substituting substance is added before or during the reaction to deposit byproduct hydrochloric acid as a salt, and any substance can be used without limitations as long as it removes hydrochloric acid and suppresses the reaction. Among them, when morpholine is used as shown in Examples, a product having high substitution degree can be obtained. In step 3) , the reaction temperature is 50-250 ^°Q and preferably 80-150 ^°C The reaction time is advantageously more than 24 hours and is determined depending on the reaction rate of each substitution reaction. If the reaction temperature is less than 50 ^°C the reaction will not smoothly progress, resulting in a reduction in substitution efficiency, and if the reaction temperature is more than 250 ^°Q a chlorine decomposition reaction will occur to form double bonds at the polymer main chain, thus making the polymer color black and deteriorating the mechanical properties of the polymer. To set high reaction temperature in atmospheric pressure conditions, the boiling point of the solvent is important, and the solvent can easily dissolve the reactants and the product at the same time. As this solvent, toluene, xylene, ethylbenzene, tetrahydrofuran, dioxane, alkyleneglycol dimethylether such as alkyleneglycol dimethylether, morpholine, N-methyl morpholine and N-ethyl morpholine can be used alone or in a mixture of two or more thereof. Also, when polar aprotic solvents such as acetonitrile are used according to the kind of amine and the like to be attached, the substitution degree of chlorine can be increased. Furthermore, as a method for increasing reaction rate, a method of conducting the reaction at increased pressure to increase the reaction temperature above the boiling point of a solvent is very useful.

Step 4) is a step of removing solid salts in a reactor. In this step, salts are prepared using a method capable of well conserving substituents and are removed using an appropriate method such as a centrifugation method, and unreacted material is separated out using an appropriate method selected depending on the kind thereof. Methods of removing salts include a method of precipitating and separating the salts using an appropriate device, and a method of filtering out the salts with a filter. Particularly, in the present invention, a centrifugation method is used as the method of removing the solids, so that the solids can be continuously removed to increase productivity so as to economically prepare the product. In the continuous centrifugation method, the product containing the solids is introduced into a centrifuge through the lower portion of the centrifuge while the solids are accumulated on the wall side of the centrifuge using the centrifugal force. The accumulated solids are moved to the upper portion of the centrifuge, and discharged through an outlet provided at the upper portion of the centrifuge, and the remaining solution is discharged through the central portion of the centrifuge and transferred to a step of collecting the product in the solution. Also, when a water-soluble polymer is prepared, a method of purifying the prepared polymer using water can be used. In this case, a well-purified modified polymer can be obtained by removing some of the solvent from the product, adding water to the product, and azeotropically distilling the solution to remove unreacted material.

In step 5) of removing the solvent to collect the modified polymer, conventional solvent recovery devices can be used to recover and recycle the solvent. Through the above-described steps, chlorine attached to polymers is substituted with an amine group, ester group, sulfide group, ether group, hydroxyl group, or mixtures of two or more thereof.

[Description of Drawings] FIG. 1 shows the ¹³C-NMR spectrum of a product obtained in Example 1. [Mode for Invention]

Hereinafter, the preparation methods according to the present invention will be described in detail with reference to examples. It is to be understood, however, that these examples are not to be construed to limit the scope of the present invention.

Example 1: polyvinyl chloride (PVC) + MOP

4,000 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 200 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added

into a 5-liter reactor, dissolved at 50 ^°C and then allowed to react at 120 ^°C for 3 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C, 10 torr) , thus obtaining a product. The results of elementary analysis of the product were as follows: N; 10.25%, C; 62.72%, H; 9.468%, and C/N weight ratio = 6.1. The product was dissolved in a D2O/DC1 solvent, and the 13C NMR spectrum thereof was measured with the Bruker FT 500 MHz NMR Spectrometer using acetone-d6 as a standard material (see FIG. 1). In FIG. 1, peaks by morpholine substitution were shown at 43 ppm and 64 ppm.

Example 2: Polyvinyl chloride (PVC) + DETA in MOP

4000 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 200 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 5-liter reactor, and dissolved at 50 ^°C . 400 parts by weight of diethylenetriamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 100 ^°C for 5 days. The reaction solution was well dispersed in distilled water, and is completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (150 ^°C, 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 13.55%, C; 61.50%, H; 10.51%, and C/N weight ratio = 4.5. Example 3: Purification method using water

The reaction solution prepared according to the method of Example 2 was placed in a rotary evaporator, and morpholine was removed therefrom until some fluidity remained. The remaining material was added slowly into 2000 parts by weight of distilled water and dispersed therein. 1000 parts by weight of a 10% NaOH aqueous solution was added to the dispersion, stirred at room temperature for 1 hour, filtered in a bag filter, and then washed several times with distilled water. Herein, unreacted amine and salt were washed out, and the product polymer remained in the bag. The polymer was transferred into a beaker and adjusted to pH 3-6 with a 35% HCl aqueous solution, thus obtaining a polymer product dissolved in water.

Example 4: Improvement of color using antioxidant This Example 4 was carried out in the same manner as in Example 2, except that 0.2 parts by weight (0.1% based on PVC) of 1, 1, 3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane- (Chemische Werke Lowi, Lowinox CA 22) was added as an antioxidant. The mixture was allowed at 100 ^°C for 5 days, and then the color of the reaction solution was definitely improved compared to Example 2. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. Example 5: Polyvinyl chloride (PVC) + EDA in MOP at 100 ^°C

50 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 3 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 100- mL reactor, and dissolved at 50 ¹C. β parts by weight of ethylenediamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 100 ^°C for 5 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and

the remaining material was dried in vacuum (120 ^°C, 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 13.06%, C; 62.59%, H; 10.23%, and C/N weight ratio = 4.8.

Example 6: Azeotropic distillation of polyvinyl chloride (PVC) + EDA The reaction solution prepared according to the method of Example 5 was placed in a rotary evaporator, and morpholine and ethylenediamine were removed therefrom until some fluidity remained. The remaining material was dispersed in 2000 parts by weight of distilled water. The dispersion was azeotropically distilled in the rotary evaporator to remove the remaining amine. The residue was adjusted to pH 3-6 with a 35% HCl aqueous solution, thus obtaining a polymer product dissolved in water.

Example 7: Polyvinyl chloride (PVC) + EDA in MOP at 70 ^"C 50 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 3 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 100- mL reactor, and dissolved at 50 "C. 6 parts by weight of ethylenediamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 70 ^°C for 3 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and

the remaining material was dried in vacuum (120 ^°C , 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 12.82%, C; 66.8%, H; 10.39%, and C/N weight ratio = 5.2.

Example 8: Polyvinyl chloride (PVC) + EDA in MOP at 80 ^°C 50 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 3 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 100- mL reactor, and dissolved at 50 ^°C . 6 parts by weight of ethylenediamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 80 ^"C for 6 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C , 10 torr), thus obtaining a product. The results of elementary analysis of the products were as follows: N; 14.50%, C; 55.77%, H; 10.10%, and C/N weight = 3.8.

Example 9: Polyvinyl chloride (PVC) + NH3 in MOP at

120 ^°C 300 parts by weight of morpholine (Samchun Pure Chemical

Co., Korea) and 15 parts by weight of PVC (polyvinyl chloride;

P-700, Hanwha Petrochemical Co., Korea) were added into a 500- mL high-pressure reactor (Autoclave Engineers Inc.) and dissolved at room temperature. 40 parts by weight of ammonia

(NH₃) was charged into the reactor with stirring, valves communicating with the reactor were all closed, and the mixture was stirred at a reaction temperature of 120 ^"C for 2 days. The reactor was cooled to room temperature, and excess gas was vented. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum

(120 ^°C, 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as -follows: N; 10.03%, C; 68.71%, H; 9.778%, and C/N weight ratio = 6.8. Example 10: Polyvinyl chloride (PVC) + NH₃ in THF/NMM at

140 ^°C

220 parts by weight of tetrahydrofuran (Samchun Pure Chemical Co., Korea) and 15 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 500-mL high-pressure reactor (Autoclave Engineers Inc.) and dissolved at room temperature. 80 parts by weight of N- methylmorpholine (Daejung Chemical & Metals Co. Ltd.) was added thereto, 40 parts by weight of ammonia (NH₃) was charged into the reactor with stirring, valves communicating with the reactor were all closed, and the mixture was stirred at a reaction temperature of 140 ^°C for 2 days. The reactor was cooled to room temperature, and excess gas was vented. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C, 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 9.76%, C; 68.97%, H; 8.352%, C/N weight ratio = 7.1.

Example 11: Polyvinyl chloride (PVC) + NH₃ in THF at

150 ^°C 250 parts by weight of tetrahydrofuran (Samchun Pure Chemical Co., Korea) and 10 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 500-mL high-pressure reactor (Autoclave Engineers Inc.) and dissolved at room temperature. 30 parts by weight of triethylamine (Samchun Pure Chemical Co., Korea) was added thereto, 40 parts by weight of ammonia (NH₃) was charged into the reactor with stirring, valves communicating with the reactor were all closed, and the mixture was stirred at a

reaction temperature of 150 ^°C for 4 days. The reactor was cooled to room temperature, and excess gas was vented. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C , 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 10.28%, C; 75.08%, H; 9.11%, and C/N weight ratio = 7.3.

Example 12: Polyvinyl chloride (PVC) + PDA in MOP at

70 ^°C

3000 parts by weight of N-methylmorpholine (Daejung Chemical & Metals Co. Ltd.) and 150 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 5-L reactor and dissolved at 50 ^°C . 1,000 parts by weight of 1, 2-propylenediamine (BASF) and 150 parts by weight of CaO (Samchun Pure Chemical Co., Korea) were added thereto, and the mixture was allowed to react at 120 ^°C for 5 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C , 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 14.42%, C; 67.97%, H; 10.22%, and C/N weight ratio = 4.7. Example 13: Polyvinyl chloride (PVC) + PDA in THF/AcCN at

70 ^°C

30 parts by weight of tetrahydrofuran (Samchun Pure Chemical Co., Korea) and 2 parts by weight of PVC (polyvinyl chloride; P-700, Hanwha Petrochemical Co., Korea) were added into a 100-mL reactor and dissolved at 50 ^"C . 30 parts by weight of acetonitrile was added slowly thereto, and the mixture was stirred to make a clear solution. To the solution, 10 parts by weight of 1, 2~propylenediamine (BASF) and 2 parts by weight of CaO (Samchun Pure Chemical Co., Korea) were added and the mixture solution was allowed to react at 60 ^"C for 5 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and

the remaining material was dried in vacuum (120 ^°C , 10 torr) , thus obtaining a product. The results of elementary ^• analysis of the products were as follows: N; 25.07%, C; 62.76%, H; 8.59%, and C/N weight ratio = 2.5.

Example 14: Chlorinated polypropylene (16LP) + EDA in MOP at 100 ^°C

500 parts by weight of morpholine (Samchun Pure Chemical

Co., Korea) and 50 parts by weight of chlorinated polypropylene (16-LP, Toyo Kasei) were added into a 1-L reactor and dissolved at 50 ^°C . 100 parts by weight of ethylenediamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 100 ^°C for 4 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^"C, 10 torr), thus obtaining a product. The results of elementary analysis of the products were as follows: N; 7.71%, C; 64.72%, H; 11.25%, and C/N weight ratio = 8.4.

Example 15: Chlorinated polypropylene (13LP) + EDA in MOP

at 100 ^°C 500 parts by weight of morpholine (Samchun Pure Chemical Co., Korea) and 50 parts by weight of chlorinated polypropylene (lβ-LP, Toyo Kaεei) were added into a 1-L

reactor and dissolved at 50 "C . 100 parts by weight of ethylenediamine (Samchun Pure Chemical Co., Korea) was added thereto and the mixture was allowed to react at 100 ^°C for 5 days. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum (120 ^°C , 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 9.04%, C; 63.31%, H; 11.9%, and C/N weight ratio = 7.0.

Example 16: Paraffin chloride (C₂₃H₄1CI7) + MOP at 130 ^°C

50 parts by weight of morpholine (Samchun Pure Chemical

Co., Korea) and 3 parts by weight of paraffin chloride (C₂₃H₄₁CI₇; Shinwon Chemical, China) were added into a 100-mL reactor, dissolved at room temperature and then allowed to react at 130 ^°C for 1 day. The reaction solution was well dispersed in distilled water and was completely dissolved in a

3% HCl aqueous solution. The reaction solution was mixed with solid NaOH at room temperature, stirred for 1 hour, and then centrifuged at 5,000 rpm for 20 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum

(120 ^"C , 10 torr) , thus obtaining a product. The results of elementary analysis of the products were as follows: N; 8.699%, C; 59.59%, H; 10.35%, and C/N weight ratio = 6.8.

Example 17

5.6 g of CPP 13-LP (Toyo Kasei; elementary analysis: C;

61.3%, H; 9.6%, Cl; 26%, N; 0%) was dissolved in 100 g of toluene, 20 g of morpholine was added thereto. The solution was stirred at 100 ^°C for 24 hours. From 1 hour after stirring, the reaction material was well dissolved to become a very clear transparent solution. After 24 hours of the reaction, 100 g of water containing 10 g of caustic soda was added thereto and the solution was strongly stirred. All the toluene and a portion of water were removed with a rotary evaporator to produce a light yellow elastic solid. A step of washing the elastic solid with 200 g of water was repeated five times to remove unreacted amine compounds and salts. After the remaining solvent was removed with the rotary evaporator, the residue was dried in vacuum to prepared morpholine-modified CPP. The results of elementary analysis of the product were as follows: C; 64.5%, H; 10.2%, N; 2.6%. This suggests that amine compounds were introduced into the product. 10 parts by weight of the above-prepared CPP-modified resin and 90 parts by weight of polypropylene resin (720, Hyundai Petrochemical Co., Ltd.) were extruded through a twin screw extruder to prepare pellets. The pellets were press-

molded at 185 ^°C to produce a sheet. Meanwhile, a dye bath was prepared by adding 0.013 parts by weight (0.013% owf) of Lumacron Yellow E3G 200% dye, 0.3 parts by weight (0.3% owf) of Paianil Red FD-BDY 200% dye and 1.7 parts by weight (1.7% owf) of Dianix Blue FBLE 100% dye to distilled water, adjusting the dye solution to pH 4-4.5 with glacial acetic acid and then adding 0.3 parts by weight (0.3% owf) of a dispersing agent (Sunsolt RM-340) to the dye solution. The above-prepared sheet was dyed in 3000 parts by weight of the above-prepared dye bath in the Mathis dyeing machine at 60 ^°C for 30 minutes and at 130 ^°C for 20 minutes, and the dyed material was washed with distilled water at 80 ^°C . The dyed material was reduced in a bath containing caustic soda 1 g/1 and NaHSO₃ (sodium hydrosulfite) 2 g/1 at 80 ^°C for 20 minutes, washed with water and then dried, thus obtaining a dyed sheet. As a result, the sheet made of the resin composition according to the present invention was observed to have an excellent color concentration compared to a sheet prepared from polypropylene resin and CPP in place of said CPP modified resin, and a sheet prepared from polypropylene resin alone, suggesting that the sheet made of the resin composition according to the present invention had very excellent dyeing ability. Thus, it could be seen that the modified chlorinated polypropylene resin improved the printability of polyolefin resin while having excellent compatibility. Example 18: Polyvinyl chloride (PVC) + 3-dimethylamino propylamine (DMAPA)

PVC (polyvinyl chloride, P-700, Hanwha Petrochemical Co., Korea) was dissolved in 200 parts by weight of ethyleneglycol dimethylether at 80 ^°C . To this solution, 50 parts by weight of 3-dimethylaminopropylanaine was added, and the mixture was refluxed in a 500-mL round-bottom flask at 100 ^°C for 12 hours. The reactor was cooled to room temperature, and the reaction solution was centrifuged at 5,000 rpm for 30 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum, thus obtaining a product. The elementary analysis of the product showed that the product had a nitrogen content of 2.1%, suggesting that amine was introduced into the product. Example 19: Polyvinyl chloride (PVC) + morpholine

PVC (polyvinyl chloride, P-700, Hanwha Petrochemical Co., Korea) was dissolved in 200 parts by weight of morpholine, and the mixture was allowed to react at 110 ^°C for 24 hours. The reaction solution was well dispersed in distilled water and was completely dissolved in a 3% HCl aqueous solution. The reaction solution was cooled to room temperature, and a solution of 20 parts by weight of caustic soda in 40 parts by weight of water was added thereto. The mixture solution was stirred at 100 ^°C for 1 hour, and 40 parts by weight of CaO was added thereto, followed by stirring for 1 hour. The reaction solution was centrifuged at 5,000 rpm for 30 minutes. The supernatant was collected, the solvent was removed therefrom using a rotary evaporator, and the remaining material was dried in vacuum 120 ^°C , 10 torr, thus obtaining a modified PVC resin. The results of elementary analysis of the product were as follows: N; 11.17%, C; 62.41%, H; 9.21%, and C/N weight ratio = 5.6.

Example 20: CPP + KOH + CaO

350 parts by weight of dioxane, 350 parts by weight of isobutanol, 40 parts by weight (0.30mol%) of chlorinated polypropylene (13-LP, Toyo Kasei) (0.30mol%), 28 parts .by weight (0.50mol%) of KOH and 28 parts by weight (0.50 mol%) of CaO were added into a 1-L round-bottom- flask and stirred at 100 "C for 24 hours. The reaction solution was cooled to 50 ^°C and centrifuged at 5,000 rpm for 30 minutes. The supernatant was collected and the solvent was removed therefrom using a rotary evaporator, thus obtaining a product. The product showed a strong peak at 3550-3660 cm^"1 in FT-IR spectrum, suggesting that a hydroxyl group was introduced into the product. [industrial Applicability]

As described above, according to the inventive method of substituting the chlorine of chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride or polyvinyl chloride copolymer, it is possible to prepare chlorine- substituted modified chlorinated polypropylene, modified chlorinated polyethylene, modified polyvinyl chloride or modified polyvinyl chloride by amine compounds in a simple and effective manner. Also, the modified polymers have very improved dyeability and printability. Moreover, when the modified polymers contain amine compounds having various functions, including UV-shielding function, antistatic function and antioxidant function according to the functional groups of the amine compounds, the modified polymers can be used as various additives, including UV-shielding agents, antioxidants, flame retardants, antistatic agents and sequestering agents. In addition, cationic polymer solutions having an increased substitution degree have low preparation cost, and thus can substitute for the prior polyamin.es, which have been used in water treatment, papermaking, adhesive applications, etc.

According to the present invention, chlorine attached to polymers can be substituted with amine, ammonia, hydroxyl group or a mixture of two or more thereof, and a desired polymer can be designed by regulating the ratio of said substituents .

Claims

[CLAIMS]

[Claim l]

A method for preparing a modified polymer by substituting 1-99 mol% of the chlorine atoms of a chlorine-containing polymer, the method comprising the steps of: dissolving the chlorine-containing polymer in a solvent; mixing the solution with a chlorine-substituting substance and a reaction- promoting substance for removing byproduct hydrochloric acid; and heating the mixture to allow it to react.

[Claim 2]

The method of Claim 1, which further comprises a step of removing produced solid salts with the reaction-promoting substance after the reaction, a step of removing the solvent to recover the modified polymer.

[Claim 3]

The method of Claim 1, wherein the solvent is one or a mixture of two or more selected from the group consisting of toluene, xylene, ethylbenzene, acetonitrile, alkyleneglycol dialkylether, tetrahydrofuran, dioxane, morpholine, N-alkyl morpholine, and morpholine.

[Claim 4]

The method of Claim 2, wherein the solids are separated by centrifugation, precipitation or filtration.

[Claim 5] The method of Claim 1, wherein the chlorine-containing polymer is one or more selected from the group consisting of paraffin chloride, chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride, and polyvinyl chloride copolymer.

[Claim 6]

The method of Claim 1, wherein the chlorine-substituting substance is amine, ammonia, metal hydroxide, or a mixture of two or more thereof.

[Claim 7]

The method of Claim 6, wherein- the metal hydroxide is one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

[Claim 8]

The method of Claim 1, wherein the substitution reaction is conducted in a high-pressure reactor.

[Claim 9] The method of Claim 1, wherein the reaction-promoting substance is a substance capable of removing reaction byproduct hydrochloric acid and is one or a mixture of two or more selected from triethylamine, trimethylamine, triethylenediamine, N-alkyl morpholine, morpholine, metal hydroxide, metal carbonate, metal oxide, and metal carboxylate. [Claim 10]

The method of Claim 1, wherein metal oxide is added during the reaction to remove water so as to reduce an elimination reaction of hydrochloric acid from the chlorine- containing polymer, so that the color of the modified polymer is not changed. [Claim ll]

The method of 10, wherein the metal oxide added during the reaction is at least one selected from the group consisting of magnesium oxide, calcium oxide, strontium oxide, and barium oxide.

[Claim 12]

The method of Claim 1, wherein an antioxidant is additionally used in the mixing step.

[Claim 13]

A modified polymer, which is prepared according to the method of any one of Claims 1 to 12 and is used as an antistatic agent, an adhesion improver, a dyeability improver, an antioxidant, a UV stabilizer, a flame retardant or a printability improver.

[Claim 14]

A modified polymer, which is prepared according to the method of any one of Claims 1 to 12 and is used as a water- treating agent, a paper-treating agent, an epoxy resin-curing agent, an urethane resin-curing agent or an adhesive agent.

[Claim 15]

A formed article, which contains the modified polymer of Claim 14 and is any one selected from the group consisting of fibers, films, sheets and molded products.

[Claim 16]

The modified article of Claim 14, which has a C/N weight ratio of 1.7-7.

[Claim 17]

The modified article of Claim 16, which has a C/N weight ratio of 1 . 7-3 . 5 .

[Claim 18 ]

An aqueous salt solution of inorganic acid o r organic acid of the modified polymer of Claim 16.

[Claim 19] The aqueous salt solution of Claim 18, wherein, the acid is selected from hydrochloric acid, sulfuric acid, acetic acid and formic acid.

[Claim 2θl

The modified polymer of Claim 14, which is a modified polymer partially substituted with morpholine.