KR101875153B1 - Vinylchloride based resin composition and method for preparing the same - Google Patents
Vinylchloride based resin composition and method for preparing the same Download PDFInfo
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- KR101875153B1 KR101875153B1 KR1020150189623A KR20150189623A KR101875153B1 KR 101875153 B1 KR101875153 B1 KR 101875153B1 KR 1020150189623 A KR1020150189623 A KR 1020150189623A KR 20150189623 A KR20150189623 A KR 20150189623A KR 101875153 B1 KR101875153 B1 KR 101875153B1
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- plasticizer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/68—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Abstract
The present invention relates to a vinyl chloride resin composition and a method for producing the same, and more particularly, to a vinyl chloride resin composition which is internally plasticized so that a molded article can be processed without using a separate plasticizer and a method for producing the same.
Description
The present invention relates to a vinyl chloride resin composition and a method for producing the same, and more particularly, to a vinyl chloride resin composition which is internally plasticized so that a molded article can be processed without using a separate plasticizer and a method for producing the same.
The vinyl chloride resin is one of the five general-purpose thermoplastic resins produced by suspension polymerization or emulsion polymerization, which is a homopolymer of vinyl chloride and a copolymer containing 50% or more of vinyl chloride. Such a vinyl chloride resin has a special function such as a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, a viscosity depressant, titanium dioxide (TiO 2 ) It is used in a wide range of fields such as flooring, wallpaper, tarpaulin, artificial leather, toys, automobile undercoating and so on by coating and mold coating molding process in the form of plastisol by mixing additives.
Since most of the vinyl chloride resin is applied to products directly contacting the human body, efforts are being made to provide environmentally friendly vinyl chloride resin compositions in the field of vinyl chloride resins. Among them, products using vinyl chloride resin are used in order to impart processability to the vinyl chloride resin in the production process. Dioctyl phthalate (DOP), diisooctyl phthalate (DIOP) and diethylhexyl phthalate Di-2-ethylhexyl phthalate (DEHP). These phthalate plasticizers are endocrine disrupters that interfere with or disrupt hormone action in humans. They are suspected to be environmental hormones. There is a regulatory movement. Recently, an example of using a non-phthalate plasticizer instead of a phthalate plasticizer has been reported.
For example, Korean Unexamined Patent Publication No. 2008-0105341 discloses the use of DOTP (Di-octyl terephthalate), which is a non-phtalate based plasticizer, alone or in combination with DINP (Di-isononyl phthalate). However, such a plasticizer or plasticizer mixture has poor gelling properties and poor foaming properties, and the plasticizer gradually migrates to the outside of the vinyl chloride resin over time, or the releasing property is poor.
Therefore, there is a need for research on a vinyl chloride resin composition which does not require a plasticizer or which can be plasticized only by using a small amount of a plasticizer.
As a result, the present inventors have made intensive efforts to solve the above problems. As a result, it has been confirmed that internal plasticization can be performed even when a specific monomer is used together with a vinyl chloride monomer without using a plasticizer, Respectively.
The present invention provides an environmentally friendly vinyl chloride resin composition which is internal plasticized without use of a plasticizer and has excellent processability and is excellent in transparency of a molded workpiece, and a method for producing the same.
The present invention provides a vinyl chloride resin composition comprising a copolymer of a vinyl chloride monomer and at least one comonomer selected from the group consisting of compounds represented by the following Formulas 1 to 3:
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 and 2,
x to z are independently of each other an integer of 1 to 10;
The present invention also relates to a process for producing a vinyl chloride resin comprising polymerizing a monomer mixture comprising a vinyl chloride monomer and at least one comonomer among the compounds represented by the above formulas 1 to 3 in the presence of an initiator to produce a vinyl chloride resin, A method for producing a vinyl resin composition is provided.
According to the vinyl chloride resin composition of the present invention, internal plasticization is performed without using any additional plasticizer, so that the processability is excellent and the transparency of the processed molded article is superior to that in the case of using the conventional internal plasticizatable monomer, Can be used in various molded articles without any limitation.
The vinyl chloride resin composition of the present invention includes a copolymer of a vinyl chloride monomer and at least one comonomer among the compounds represented by the following general formulas (1) to (3):
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 and 2,
x to z are independently of each other an integer of 1 to 10;
The method for producing a vinyl chloride resin composition according to the present invention comprises polymerizing a monomer mixture comprising a vinyl chloride monomer and at least one comonomer among the compounds represented by the above formulas 1 to 3 in the presence of an initiator to form a vinyl chloride resin . ≪ / RTI >
Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Hereinafter, the present invention will be described in more detail.
The vinyl chloride resin composition according to an embodiment of the present invention includes a copolymer of a vinyl chloride monomer and at least one comonomer among the compounds represented by the formulas (1) to (3).
Vinyl chloride monomer
The vinyl chloride monomer refers to a monomer of vinyl chloride alone or a mixture of vinyl chloride with other monomer copolymerizable with vinyl chloride. Examples of the copolymerizable monomer include olefins such as ethylene, propylene and butene; Vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate and vinyl stearate; Vinyl ethers having alkyl groups such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and launyl vinyl ether; Vinylidene halides such as vinylidene chloride; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride and itaconic anhydride, and acid anhydrides thereof; Unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate and butyl benzyl maleate; Aromatic vinyl compounds such as styrene, a-methylstyrene, and divinylbenzene; Unsaturated nitriles such as acrylonitrile; Or diallyl phthalate. These may be used singly or in combination of two or more.
The vinyl chloride monomer may be included in an amount of about 30 to about 95% by weight, and preferably about 50 to about 90% by weight based on the total monomer weight. Wherein the total monomers are all monomers used in the formation of the copolymer. When the vinyl chloride monomer is used within the above-mentioned content range, physical properties required for the vinyl chloride resin may be realized.
The comonomer represented by the general formulas (1) to (3)
In order to produce a molded article that can be used in various applications without adding a plasticizer to the vinyl chloride resin composition, internal plasticization of the vinyl chloride resin is required. Herein, the term "internal plasticization" refers to a case in which plasticity is realized from the molecular structure of a vinyl chloride resin, unlike the external plasticization in which a material is added from the outside after plasticizing the vinyl chloride resin to give plasticity It says.
Therefore, in order to internalize the vinyl chloride resin, the present invention uses one selected from the compounds represented by the above formulas (1) to (3) capable of copolymerizing with the vinyl chloride monomer or a combination thereof.
Specifically, the compound represented by Formula 1 is a poly (ethylene glycol) phenyl ether acrylate compound, and the compound represented by Formula 2 is a compound represented by Formula 1, Specifically, it is a polyethylene glycol phenyl ether acrylate compound in which hydrogen at the para position of ethylene oxide is substituted with an alkyl group. The compounds represented by the formulas (1) and (2) can have various structures depending on the number of repeating ethylene oxide repeating units (x in the formula (1) and y in the formula (2) and / or the number of the alkylene repeating units . In addition, the compound represented by the general formula (3) is bis (2-ethylhexyl) maleate.
The compounds represented by the above general formulas (1) to (3) contain vinyl groups and can copolymerize with the vinyl chloride resin. The copolymer having repeating long backbone can exhibit an internal plasticizing effect. For example, the compounds represented by the general formulas (1) to (3) are copolymerized with vinyl chloride monomers to increase the free volume in the copolymer molecules prepared by extending the main chain length, Can be weakened. Accordingly, the vinyl chloride resin containing the copolymer can exhibit flexibility at room temperature.
Therefore, in the case of a vinyl chloride resin composition comprising a copolymer prepared by using at least one of the comonomers represented by Chemical Formulas 1 to 3, the use of an external plasticizer is not required due to the internal plasticizing effect have. Therefore, not only environmental problems caused by the phthalate plasticizer are caused, but migration of the non-phthalate plasticizer may not occur.
Internal plasticizations can also be achieved by copolymerization of unsaturated group-containing compounds such as ethyl acrylate, butyl acrylate and the like with the vinyl chloride monomer. However, when processed by the above compounds, the point / The molded article may tend to sticky and the free volume in the copolymer molecules may not be sufficiently increased due to the non-bulky structure of the compounds, resulting in poor transparency of the molded article. In addition, when plasticized by the above-mentioned compounds, mechanical properties such as hardness and tensile strength of a molded article may be lowered as compared with the case of using an external plasticizer.
However, when one of the comonomers represented by the above formulas (1) to (3) is used, the low Tg of the comonomer and the bulky structure capable of sufficiently increasing the free volume in the copolymer molecules, It is possible to produce a molded article having significantly improved transparency and excellent mechanical properties as compared with the case of using acrylate or the like. In addition, a molded article having no deterioration in transparency and mechanical properties can be produced even when an external plasticizer is used.
The weight-average molecular weight of the compound represented by the formula (1) From about 150 g / mol to about 600 g / mol, for example from about 190 g / mol to about 560 g / mol. The weight average molecular weight of the compound represented by Formula 2 may be about 250 g / mol to about 850 g / mol, for example, about 280 g / mol to about 830 g / mol. When the weight average molecular weight of the compounds represented by the above formulas (1) and (2) is within the above range, the workability of the vinyl chloride resin can be improved by a sufficient internal plasticizing effect. The molecular weights of the compounds represented by the formulas (1) and (2) can be adjusted according to the values of x, y, and z, which are the numbers of repeating units.
One or more comonomers among the compounds represented by the above formulas (1) to (3) may be included in an amount of about 5 to about 70% by weight, and preferably about 10 to about 50% by weight, based on the total monomer weight . When the total amount of the compounds or compounds represented by the above formulas (1) to (3) is used within the above range, internal vinylation of the vinyl chloride resin may be possible, and the physical properties of the molded article using the resin may not be deteriorated.
According to one embodiment, the vinyl chloride resin composition may further include a suspending agent, an emulsifying agent, or a dispersing agent, which is added as needed in the polymerization step.
The dispersing agent may include polyvinyl alcohol having a degree of saponification of 40% or more, cellulose, gelatin, acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, succinic acid polymer, Can be used.
The suspending agent may be selected from the group consisting of polyvinylpyrrolidone (PVP), poly [(vinyl alcohol) -co- (vinyl acetate)], poly gums, cellulose ethers, cellulose esters, or combinations thereof.
As the emulsifier, an anionic emulsifier, a nonionic emulsifier or a mixture thereof may be used. The anionic emulsifier may be an alkali metal salt or ammonium salt of a C 6 -C 20 fatty acid, an alkali metal salt or ammonium salt of a C 6 -C 20 alkylsulfonic acid, an alkali metal salt or ammonium salt of a C 6 -C 20 alkylbenzenesulfonic acid, But are not limited to, alkali metal salts or ammonium salts of the alkali metal salts or ammonium salts of 6-20 alkyl disulfonic acid diphenyl oxides, or combinations thereof. The nonionic emulsifier may be an alcohol having 6 to 20 carbon atoms, polyethylene oxide, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan monolaurate, polyvinyl alcohol, polyethylene glycol, , But is not limited thereto.
The suspension or emulsifier may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the total monocotyls. When the suspending agent or emulsifying agent is used within the above-mentioned content range, the polymerization between the monomers can proceed effectively.
According to one embodiment, the vinyl chloride resin composition may further include a plasticizer, i.e., an external plasticizer. As described above, the vinyl chloride resin composition may not require a separate plasticizer due to internal plasticization, but may further include a small amount of external plasticizer depending on the application. Here, the external plasticizer means a substance that is not copolymerized with the vinyl chloride resin but exists separately.
Examples of the plasticizer include those generally used in the art without any particular limitation. Examples of the plasticizer include adipic acid, dimethyl adipate, diethyl adipate, diisobutyl adipate, di-n-hexyl adipate, Adipic acid-based plasticizer containing an alkyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, amide ester, azelate, benzoate, benzotriazole, glutarate, glycerol ester, glycol Ester, glycol, glycolate, hexahydrophthalate, isobutyrate, and isophthalate may be used alone or in admixture of one or more. By adding the plasticizer, flexibility can be imparted to the plastisol, and the viscosity can be adjusted to a suitable level for processing.
Specifically, the plasticizer may include a phthalate plasticizer or a non-phthalate plasticizer. For example, DOP or DOTP. Accordingly, when an environmental problem is considered, non-phthalate-based DOTP can be used, and phthalate-based DOP can be used in terms of improvement in physical properties.
The plasticizer may be included in an amount of about 5 to about 50 parts by weight, preferably about 10 to about 30 parts by weight, based on 100 parts by weight of the resin produced by the total monomer. The content of the plasticizer used is significantly lower than that of a plasticizer when only an external plasticizer is used without using the compounds represented by the chemical formulas (1) to (3), thereby preventing environmental problems and deterioration of physical properties.
Process for producing vinyl chloride resin composition
On the other hand, the above-mentioned vinyl chloride resin composition is obtained by polymerizing a monomer mixture containing a vinyl chloride monomer and at least one comonomer among the compounds represented by the formulas (1) to (3) in the presence of an initiator to produce a vinyl chloride resin The method comprising the steps of:
The method for producing the vinyl chloride resin composition according to one embodiment will be described in detail as follows.
First, the monomer mixture may be polymerized in the presence of an initiator to prepare a slurry containing the copolymer. Next, after the unreacted monomers are removed from the slurry, the slurry from which the unreacted monomers are removed may be dehydrated and dried to produce a vinyl chloride resin.
In the method for producing a vinyl chloride resin composition, the description of the vinyl chloride monomer and at least one comonomer among the compounds represented by the formulas (1) to (3) is as described above.
At this time, one or more comonomers among the compounds represented by the above-mentioned formulas (1) to (3) may be introduced simultaneously with the vinyl chloride monomer or may be continuously introduced during polymerization. The continuous introduction may be up to about 80% of the reaction time. For example, if the polymerization reaction is carried out for 6 hours, the continuous introduction may be performed for 4 hours from the beginning of the reaction or for 5 hours from the beginning of the reaction.
The polymerization may be preferably a suspension polymerization or an emulsion polymerization. At this time, the suspension polymerization can be used as a reaction medium for the polymerization water at normal temperature or high temperature. Also, the monomers and the oil-soluble initiator may be decomposed at a predetermined temperature, for example, 50 to 70 ° C, and polymerization may proceed by a chain reaction with the vinyl chloride monomer. When the reaction conversion rate of the monomer mixture reaches a certain point, the polymerization can be terminated.
In addition, the polymerization may be carried out in the presence of a suspending agent or an emulsifying agent. The description of the suspending agent and emulsifying agent that can be used in the polymerization is as described above.
When the anionic emulsifier and the nonionic emulsifier are mixed and used as the emulsifier, the anionic emulsifier and the nonionic emulsifier may be mixed in a weight ratio of about 1: 0.5 to about 1: 200, May be mixed in a weight ratio of 1: 2 to about 1: 50. When the anionic emulsifier and the nonionic emulsifier are mixed in the weight ratio range, the stability of the slurry can be ensured, the polymerization conversion rate can be maximized, and the polymerization reaction can be carried out from the surface of the polymerized vinyl chloride resin to the inside of the resin Heat transfer can be prevented as much as possible.
The initiator may include an oil-soluble initiator, a water-soluble initiator, or a combination thereof. The oil-soluble initiator may be at least one selected from the group consisting of t-butyl peroxyneodecanoate, diisopropyl peroxy dicarbonate, methyl ethyl ketone peroxide, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate Or combinations thereof; peroxyesters including t-butyl peroxy pivalate, t-amyl peroxy pivalate, t-hexyl peroxy pivalate, or combinations thereof; Or combinations thereof, but are not limited thereto. The water-soluble initiator may be selected from the group consisting of sulfates including potassium persulfate, ammonium persulfate, sodium persulfate, sodium bisulfate, or combinations thereof; Sodium hydrosulfite; (2,2'-azobisisobutyronitrile), 2,2'-azobis- (methyl 2-methylpropionate), 2,2'-azobis- (2,4-dimethylvaleronitrile) -Azobis- (4-methoxy-2-dimethylvaleronitrile) or a combination thereof; Or combinations thereof, but are not limited thereto.
The initiator may be used in an amount of about 0.01 to about 5 parts by weight, preferably about 0.02 to about 1.0 part by weight, based on 100 parts by weight of the total monomers. When the initiator is used within the above range of content, it is excellent in polymerization reactivity and may be advantageous to control the heat of polymerization reaction.
When the oil-soluble initiator and the water-soluble initiator are used together, they may be used in a weight ratio of about 95: 5 to about 5:95, preferably in a weight ratio of about 90: 10 to about 10: . When the oil-soluble initiator and the water-soluble initiator are mixed in the above ratio range, the polymerization time can be appropriately controlled to improve the productivity.
When both the emulsifier and the water-soluble initiator are used as additives for the polymerization reaction, the emulsifier and the water-soluble initiator can be used in a weight ratio of about 1:50 to about 50: 1, preferably about 1:20 To about 20: 1, more preferably from about 1: 1 to about 20: 1, or from about 2: 1 to about 15: 1. When an emulsifier and a water-soluble initiator are mixed in the above-mentioned ratio range, a resin having excellent glossiness can be obtained while minimizing deterioration in adhesion due to the use of an emulsifier.
According to one embodiment, a dispersant may be further included as an additive in the polymerization reaction. The dispersing agent may include polyvinyl alcohol having a degree of saponification of about 40% or more, cellulose, gelatin, acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, succinic acid polymer or a combination thereof.
The dispersant may be used in an amount of about 0.03 to about 5 parts by weight, specifically about 0.05 to about 2.5 parts by weight, based on 100 parts by weight of the total monomers. When the dispersant is used within the above-mentioned content range, it is possible to produce vinyl chloride resin particles of uniform size.
According to one embodiment, the method for producing a vinyl chloride resin composition may further include a step of mixing a plasticizer with the vinyl chloride resin. The plasticizer to be added after the completion of the polymerization reaction may further impart plasticity to the vinylated vinyl chloride resin as an external plasticizer.
The plasticizer may be used in an amount of about 5 to about 50 parts by weight, for example about 10 parts by weight to about 30 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the plasticizer is used in the above range, the content of the external plasticizer is less than half that of the external plasticizer, so that the migration phenomenon may be reduced but the physical properties may not be deteriorated.
According to another aspect of the present invention, there is provided a molded article comprising the vinyl chloride resin composition. The molded product may be prepared by further adding an additive such as a stabilizer, a filler, and / or a foaming agent to the vinyl chloride resin composition according to the use thereof.
Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
<Examples>
Production of vinyl chloride resin composition
[Example 1]
After the oxygen inside the 5 L reactor was removed by using a vacuum pump, 980 g (70 wt%) of vinyl chloride monomer, Phenol (EO) 4 Acrylate (formula 1, x = 4 , 70 g (5 parts by weight) of a cellulose-based suspension of 3% aqueous solution, initiator 2,2'-Azobis (2,4-dimethyl) 5 g (0.35 parts by weight) of valeronitrile (ABVN) was mixed with 2100 g of deionized water to initiate polymerization.
The reaction was continued for 5 hours while maintaining the reactor temperature at 58 캜. When the reactor pressure was lowered to 2.0 kg / cm 2 from the initial stage of the polymerization, the polymerization was stopped and unreacted monomers were recovered and the polymerization was terminated. The polymerized slurry was dehydrated and dried to obtain a vinyl chloride resin.
[Example 2]
Except that Phenol (EO) 4 Acrylate (Formula 1, x = 4, weight average molecular weight: 324 g / mol) initially charged in Example 1 was continuously charged until completion of the reaction after the completion of the reaction, A vinyl chloride resin was obtained.
[Example 3]
Except that 1190 g (85% by weight) of vinyl chloride monomer and 210 g (15% by weight) of phenol (EO) 4 acrylate (formula 1, x = 4, weight average molecular weight 324 g / mol) A vinyl chloride resin was obtained in the same manner as in Example 1.
Then, 25 parts by weight of a plasticizer Dioctyl terephthalate (DOTP) was added to 100 parts by weight of the vinyl chloride resin thus prepared, followed by mixing with a mixer (manufactured by Hobart) for 10 minutes to obtain a vinyl chloride resin composition.
[Example 4]
A vinyl chloride resin composition was obtained in the same manner as in Example 3, except that 50 parts by weight of a plasticizer Dioctyl terephthalate (DOTP) was added to 100 parts by weight of the vinyl chloride resin in Example 3.
[Example 5]
Except that phenol (EO) 4 acrylate initially added in Example 1 was replaced with nonyl phenol (EO) 8 Acrylate (Formula 2, y = 8, z = 3, weight average molecular weight 626 g / mol) Vinyl chloride resin was obtained in the same manner as in Example 1.
[Example 6]
A vinyl chloride resin was obtained in the same manner as in Example 1 except that Phenol (EO) 4 acrylate initially added in Example 1 was replaced with Bis (2-ethylhexyl) maleate (Formula 3).
[Comparative Example 1]
After removing the oxygen inside the 5 L reactor using a vacuum pump, 1400 g (100 parts by weight) of the vinyl chloride monomer, 40 g (2.86 parts by weight) of the PVA having a degree of saponification of 70% to 95% in the 3% aqueous solution, the initiator t-amyl peroxyneodecanoate 0.40 g (0.0286 parts by weight) of t-butyl peroxyneodecanoate and 0.60 g (0.0429 parts by weight) of t-butyl peroxyneodecanoate were mixed in 2300 g of dehydration water to initiate polymerization. Thereafter, a vinyl chloride resin was obtained in the same manner as in Example 1.
Then, 25 parts by weight of a plasticizer Dioctyl terephthalate (DOTP) was added to 100 parts by weight of the vinyl chloride resin thus prepared, followed by mixing with a mixer (manufactured by Hobart) for 10 minutes to obtain a vinyl chloride resin composition.
[Comparative Example 2]
A vinyl chloride resin composition was obtained in the same manner as in Comparative Example 1 except that 50 parts by weight of a plasticizer Dioctyl terephthalate (DOTP) was added to 100 parts by weight of a vinyl chloride resin in Comparative Example 1.
[Comparative Example 3]
A vinyl chloride resin was obtained in the same manner as in Example 1, except that Butyl Acrylate was used as a monomer for internal plasticization, and the polymerization was initiated after the initiation of polymerization.
The compositions of the materials used in the above Examples and Comparative Examples are summarized in Table 1 below.
(100 parts by weight)
(Parts by weight)
Experimental Example
The average particle diameter and apparent specific gravity of the vinyl chloride resin prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured by the following methods. Next, a vinyl chloride resin composition was prepared in the form of a sheet at 170 DEG C using a roll mill, and then the sheet was pressed at 180 DEG C to prepare a specimen having a thickness of 3 mm. Hardness, tensile strength, elongation and flat plate permeability were measured by the following methods. The measurement results are shown in Table 2 below.
- Average particle size (MPS): Particle size analysis using a particle size analyzer (Malvern Mastersizer, Melbourne)
- Apparent Specific Gravity (BD): 100 g of resin is freely dropped in a 100 cc container according to ASTM D1895 and measured by weight difference
- Hardness: measured using a Shore A durometer according to ASTM D2240
- Tensile Strength and Elongation: Measured under Crosshead speed 200 mm / min using U.TM according to ASTM D638
- Flat plate transmittance: Analysis using Haze-gard Plus (BYK-Gardner)
(탆)
(g / cm 3)
(Shorea)
(kg / cm 2 )
(%)
Permeability
(%)
As shown in Table 2, the molded articles obtained by using the vinyl chloride resins of Examples 1, 2, 5 and 6, which were internally plasticized by the compound represented by Chemical Formula 1, 3, the flatness of the plate was remarkably high, indicating excellent transparency as well as excellent hardness and tensile strength.
Furthermore, the molded articles obtained using the vinyl chloride resins of Examples 1, 2, 5 and 6 exhibited similar physical properties as those of Comparative Examples 1 and 2 which used only ordinary external plasticizers.
It was also confirmed that physical properties such as hardness can be controlled by controlling the injection timing of the monomer represented by the formula (1) in the comparison of physical properties with respect to Examples 1 and 2.
In addition, Example 3 exhibited the same hardness and equivalent physical properties as those of Comparative Example 2, and thus, even if the external plasticizer content was reduced to half, the external plasticizer was obtained by internal plasticization by the monomer represented by Formula 1 It is possible to realize a molded article having the same physical properties as those used.
Claims (13)
Wherein the comonomer is contained in an amount of 5 to 50% by weight based on the total monomer weight,
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 and 2,
x to z are independently of each other an integer of 1 to 10;
The weight average molecular weight of the compound represented by Formula 1 is 150 g / mol to 600 g / mol,
The weight average molecular weight of the compound represented by Formula 2 is 250 g / mol to 850 g / mol.
Wherein the composition further comprises a suspending agent, an emulsifying agent, or a dispersing agent.
A vinyl chloride resin composition, further comprising a plasticizer.
Wherein the plasticizer comprises a phthalate plasticizer or a non-phthalate plasticizer.
Wherein the plasticizer is contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total monomers.
A method for producing a vinyl chloride resin composition, comprising the steps of: polymerizing in the presence of an initiator to prepare a vinyl chloride resin;
[Chemical Formula 1]
(2)
(3)
In the above Formulas 1 and 2,
x to z are independently of each other an integer of 1 to 10;
Wherein at least one comonomer among the compounds represented by the general formulas (1) to (3) is introduced simultaneously with the vinyl chloride monomer, or continuously introduced during polymerization.
Wherein the polymerization is a suspension polymerization or an emulsion polymerization.
Wherein the polymerization is carried out in the presence of a suspending agent or an emulsifying agent.
Further comprising a step of mixing a plasticizer with the vinyl chloride resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2564646A (en) * | 1950-02-08 | 1951-08-14 | Argus Chemical Lab Inc | Haze resistant vinyl chloride polymers |
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