Chloroethylene-based nanocomposite composition and method of preparing the same

Abstract

Disclosed are a chloroethylene-based nanocomposite composition comprising a chloroethylene-based resin; a nanoclay comprising a coupling agent bonded thereto; and at least one polymer selected from unsaturated organic acid-based resins or polycarboxylic acid-based resins, and a method of preparing the same.

Claims

1. A chloroethylene-based nanocomposite composition comprising: i) a chloroethylene-based resin formed from chloroethylene-based monomer; ii) a nanoclay comprising a coupling agent bonded thereto; and iii) at least one polymer selected from unsaturated organic acid resin or polycarboxylic acid resin, wherein an amount of the at least one polymer selected from unsaturated organic acid resin or polycarboxylic acid resin is 0.1 to 8 parts by weight based on 100 parts by weight of the nanoclay comprising the coupling agent bonded thereto, wherein the coupling agent comprises Formula 1 below:
(RO.sub.nZOXRY).sub.4-n[Formula1] wherein RO is a hydrolyzed group or a substrate-reactive group, a carbon number of R being less than 14 or 1 to 14, Z is titanium, zirconium or aluminum, X is a phosphate, pyrophosphate, sulfonyl or carboxyl-bonding functional group, R is a C.sub.14 or more, or C.sub.14 to C.sub.60 aliphatic, naphthenic or aromatic thermoplastic functional group, Y is a thermosetting functional group of aryl, methacryl, mercapto or amino, and n is an integer of 1 to 3, wherein the unsaturated organic acid resin is one or more selected from the group consisting of acrylic acid resins, methacrylic acid resins, itaconic acid resins, fumaric acid resins, maleic acid resins, succinic acid resins, oleic acid resins and gelatin, and wherein the polycarboxylic acid resin is a single polymer or a resin, a main chain of which comprises Formula 2 below: ##STR00002## wherein each of R.sub.1, R.sub.2, and R.sub.3 is hydrogen or a C.sub.1 to C.sub.5 alkyl group, M.sub.1 is hydrogen, an alkali metal, an alkali earth metal, a C.sub.1 to C.sub.10 alkylammonium group, or a C.sub.1 to C.sub.10 alkyl alcohol ammonium group, and m.sub.1 is an integer of 0 to 2.

2. The chloroethylene-based nanocomposite composition according to claim 1, wherein a particle diameter of the nanoclay comprising the coupling agent bonded thereto is 1 to 300 nm.

3. The chloroethylene-based nanocomposite composition according to claim 1, wherein the nanoclay comprising the coupling agent bonded thereto is modified with organic sulfonic acid or organic carboxylic acid.

4. The chloroethylene-based nanocomposite composition according to claim 1, wherein the coupling agent is comprised in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the nanoclay.

5. The chloroethylene-based nanocomposite composition according to claim 1, wherein the nanoclay comprising the coupling agent bonded thereto is comprised in an amount of 1 to 20 parts by weight based on 100 parts by weight of the chloroethylene-based monomer.

6. The chloroethylene-based nanocomposite composition according to claim 1, wherein the polycarboxylic acid resin is a polymer polymerized with one or more selected from the group consisting of carboxylic acid, acrylic acid, methyl(meth)acrylic acid, ethyl(meth)acrylic acid, trimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, 4-pentanoic acid and salts thereof.

7. A method of preparing the chloroethylene-based nanocomposite composition of claim 1, the method comprising: preparing a water dispersion suspension by stirring the nanoclay comprising the coupling agent bonded thereto, the at least one polymer selected from unsaturated organic acid resin or polycarboxylic acid resin, and water; preparing a mixed solution by adding a protective colloidal agent and chloroethylene- based monomer to the water dispersion suspension and mixing the same; and adding an initiator to the mixed solution and suspension-polymerizing the same.

8. The method according to claim 7, wherein the water dispersion suspension comprises 1 to 20 parts by weight of the nanoclay comprising the coupling agent bonded thereto and 0.01 to 1.5 parts by weight of the at least one polymer selected from unsaturated organic acid resin or polycarboxylic acid resin based on 100 parts by weight of water.

9. The method according to claim 7, wherein the mixed solution comprises 100 to 200 parts by weight of the water dispersion suspension, 0.001 to 5 parts by weight of the protective colloidal agent and 0.0001 to 0.5 parts by weight of the initiator based on 100 parts by weight of the chloroethylene-based monomer.

10. The method according to claim 7, wherein the protective colloidal agent is at least one selected from the group consisting of a vinyl alcohol based resin, a hydration degree of which is 30 to 98% by weight and a viscosity of a 4% aqueous solution of which is 5 to 100 cP at room temperature, cellulose, which comprises 15 to 40% by weight of a methoxy group and 3 to 20% by weight of a hydroxypropyl group and 2% aqueous solutions of which is viscosity of 10 to 20,000 cP at room temperature, and unsaturated organic acid.

11. The method according to claim 7, wherein the initiator is one or more selected from the group consisting of diacyl peroxides, peroxydicarbonates, peroxyesters, azo compounds and sulfates.

Description

EXAMPLE 1

(1) 390 kg of deionized water, 1.5 kg of polyfumaric acid as a polycarboxylic acid-based resin, and 30 kg of a nanoclay (titanium IV 2,2 (bis 2-propenolatomethyl)butanolato, tris (dioctyl) pyrophosphato-O) comprising a titanium-based coupling agent thereto and having a particle diameter of 80 nm were added to a reactor having an inner volume of 1 m.sup.3 and equipped with a reflux condenser, and then stirred for 1 hour, to prepare a water dispersion suspension.

(2) With the resultant water dispersion suspension, polyvinyl alcohol having a hydration degree of 87.5% was added in an amount of 150 g and hydroxypropylmethyl cellulose was added in an amount of 150 g to the reactor. Subsequently, 300 kg of a chloroethylene-based monomer was added thereto and then stirred for 1 hour, to prepare a solution. Subsequently, 30 g of di-2-ethylhexylperoxydicarbonate and 120 g of t-butylperoxy neodecanoate were added thereto and then suspension polymerization was initiated.

(3) In order to achieve a target average polymerization degree of 800 during an overall polymerization process, reaction was carried out while maintaining 65 C. In addition, when a polymerization reactor pressure reached 8.0 kg/cm.sup.2, 15 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl and 60 g of triethyleneglycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate as reaction terminators were added to the reactor and then unreacted monomers were collected. A resin slurry was collected from the polymerization reactor.

(4) The obtained slurry was dried in a fluidized bed dryer through a general method. As a result, a chloroethylene-based nanocomposite composition was obtained.

EXAMPLE 2

(5) Polymerization was carried out under the same conditions as in Example 1, except that 40 kg of nanoclay (Zirconium IV 2,2 (bis-2-propenolatomethyl)butanolato, tri(dioctyl)pryrophosphato-O) including a zirconium-based coupling agent bonded thereto and having a particle diameter of 120 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 1.5 kg of polymaleic acid vinyl acetate as an unsaturated organic acid resin were used, thereby obtaining a chloroethylene-based nanocomposite composition.

EXAMPLE 3

(6) Polymerization was carried out under the same conditions as in Example 1, except that 20 kg of nanoclay (di-isopropyl(oleyl)aceto aluminate, isopropyl bistearyl aluminate) having a particle diameter of 80 nm and including aluminum-based coupling agent bonded thereto instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 1.0 kg of polyacrylic acid as an unsaturated organic acid resin was used, thereby obtaining a chloroethylene-based nanocomposite composition.

EXAMPLE 4

(7) Polymerization was carried out under the same conditions as in Example 1, except that 15 kg of a nanoclay including a titanium-based coupling agent bonded thereto and having a particle diameter of 120 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 1.0 kg of polyfumaric: acid as an unsaturated organic acid resin were used, thereby obtaining a chloroethylene-based nanocomposite composition.

EXAMPLE 5

(8) Polymerization was carried out under the same conditions as in Example 1, except that 30 kg of a nanoclay including a titanium-based coupling agent bonded thereto and having a particle diameter of 40 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 200 g of polyacrylic acid were used, thereby obtaining a chloroethylene-based nanocomposite composition.

EXAMPLE 6

(9) Polymerization was carried out under the same conditions as in Example 1, except that 30 kg of a nanoclay including a titanium-based coupling agent bonded thereto and having a particle diameter of 40 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 5 kg of polyacrylic acid were used, thereby obtaining a chloroethylene-based nanocomposite composition.

COMPARATIVE EXAMPLE 1

(10) 390 kg of deionized water, 150 g of polyvinyl alcohol having a hydration degree of 78%, 120 g of polyvinyl alcohol having a hydration degree of 40% and 30 g of hydroxypropylmethyl cellulose were added batchwise to a reactor having an inner volume of 1 m.sup.3 and equipped with reflux condenser, and then 30 g of di-2-ethylhexylperoxydicarbonate and 120 g of t-butylperoxy neodecanoate were added thereto. Subsequently, in order to achieve a target average polymerization degree 800, reaction was carried cut while maintaining 65 during an overall polymerization process.

(11) When a polymerization reactor pressure reached at 8.0 kg/cm.sup.2, 15 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl and 60 g of triethyleneglycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate as reaction terminators were added to the reactor and then unreacted monomers were collected. A resin slurry was collected from the polymerization reactor. The obtained slurry was dried in a fluidized bed dryer through a general method. As a result, a chloroethylene-based resin was obtained.

COMPARATIVE EXAMPLE 2

(12) A chloroethylene-based resin was obtained under the same conditions as in Example 1, except that 20 kg of nanoclay not including coupling agent and having particle diameter of 80 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 1.0 kg of polyfumaric acid as an unsaturated organic were used.

COMPARATIVE EXAMPLE 3

(13) A chloroethylene-based resin was obtained under the same conditions as in Example 1, except that 30 kg of a nanoclay not including a coupling agent and having a particle diameter of 120 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 1.0 kg of polyfumaric acid as an unsaturated organic acid resin were used.

COMPARATIVE EXAMPLE 4

(14) Reaction was carried out under the same conditions as in Example 1, except that the unsaturated organic acid-based resin or the polycarboxylic acid-based resin was not used. However, mass scale was generated during polymerization and thus polymerization was failed, whereby property measurements were impossible.

REFERENCE EXAMPLE 1

(15) Polymerization was carried out under the same conditions as in Example 1, except that 20 kg of nanoclay including a titanium-based coupling agent bonded thereto and having a particle diameter of 40 nm instead of the nanoclay including the titanium-based coupling agent bonded thereto and having a particle diameter of 80 nm, and 15 g of polymaleic acid vinyl acetate were used, thereby obtaining a chloroethylene-based nanocomposite composition.

(16) Properties of the chloroethylene-based nanocomposite compositions prepared according to Examples 1 to 6, Comparative Examples 1 to 4 and Reference Example 1, and results of specimens thereof are summarized in Table 1 below. Measurement of polymerization degree: Measured according to ASTM D1 243-79. Measurement of apparent specific gravity: Measured according to ASTM D1 895-89. Adhered scale state: An adhered scale state in a polymerization reactor was observed with the naked eye and evaluated as follows.

(17) : Adhered scale is not observed.

(18) : Small amount of adhered scale is observed.

(19) X: Large amount of adhered scale is observed. Measurement of tensile strength: 5 parts by weight of a mixed stabilizer (WPS-60) including a thermal stabilizer and a lubricant, 1.5 parts by weight of a processing aid (PA-828) and 2 parts by weight of titanium oxide were added to a chloroethylene-based resin, based on 100 parts by weight of the chloroethylene-based resin. A resultant mixture was calendered at 185 for five minutes using a roil mill and then compressed at 185 for two minutes under a pressure of 10 K/G using a press, thereby preparing a hard specimen. An obtained specimen was subjected to tensile strength measurement according to ASTM 0638. Transparency evaluation: 4 parts by weight of a tin-based stabilizer, 1 part by weight of a processing aid (PA-910), 6 parts by weight of an impact modifier (MB872) and 0.5 parts by weight of a lubricant (SL63) were mixed with the obtained resin, based on 100 parts by weight of the resin. A resultant mixture was kneaded using a roll at 185 for five minutes, thereby obtaining a sheet. The sheet was cut, laminated, and compressed by press-molding, thereby preparing a compressed sheet. The compressed sheet was measured using a WYK-Gardner (model name: Haze-gard plus). Particle diameter: Measured using TEM.

(20) TABLE-US-00001 TABLE 1 Measured items Apparent Polymer- specific Tensile ization gravity Scale strength Units degree g/cc state kgf/cm.sup.2 Transparency Example 1 801 0.637 755 81.1 Example 2 799 0.657 780 82.6 Example 3 800 0.630 720 78.8 Example 4 803 0.617 695 79.4 Example 5 802 0.646 740 82.0 Example 6 803 0.643 785 74.6 Comparative 800 0.532 525 73.1 Example 1 Comparative 802 0.572 635 76.8 Example 2 Comparative 801 0.581 650 77.4 Example 3 Comparative Polymerization is failed Example 4 Reference Over-size X Example 1

(21) As shown in Table 1, in Examples 1 to 6 including the chloroethylene-based resin according to the present disclosure; a nanoclay comprising a coupling agent bonded thereto; and at least one polymer selected from unsaturated organic acid-based resins or polycarboxylic acid-based resins, a high apparent specific gravity is observed, adhered scale is not observed, and greatly enhanced tensile strength and transparency are exhibited.

(22) On the other hand, in Comparative Example 1 that does not include the nanoclay comprising the coupling agent bonded thereto and the unsaturated organic acid-based resin or the polycarboxylic acid-based resin, an apparent specific gravity, tensile strength and transparency are greatly deteriorated.

(23) In addition, in Comparative Examples 1 and 3 in which the nanoclay not including the coupling agent is used, an apparent specific gravity, a scale state, tensile strength and transparency are deteriorated. Furthermore, in Comparative Example 4 in which the nanoclay comprising the coupling agent bonded thereto is used, but the unsaturated organic acid-based resin or the polycarboxylic acid-based resin is not included, massive scale is generated during polymerization and thus polymerization fails.