KR20120102551A - Eco-friendly alternative plasticizer based on nanobrush structure and manufacture method of them using one-pot process - Google Patents

Abstract

PURPOSE: An environment-friendly nanobrush-type alternative plasticizer is provided to cope with environment regulations while providing excellent plasticizing effects because of excellent miscibility with PVC while preventing a leakage of PVC to outside. CONSTITUTION: An environment-friendly nanobrush-type alternative plasticizer is in chemical formula 1. In chemical formula 1, A is a moiety excluding -OH from a polyol selected from linear aliphatic polyol, cyclic aliphatic polyol, oxygen-containing linear aliphatic polyol, and oxygen containing cyclic aliphatic polyol, R is hydrogen or CaHbOcNdPe, R' is C1-10 alkyl, and C6-20 aryl or C3-10 cycloalkyl, w is 0 or 1, x is an integer from 1 or more, y is an integer form 1 or more, z is, as a number of -OH in polyol of A, an integer from 2 or more.

Description

Nano-friendly alternative plasticizer based on nanobrush structure and manufacture method of them using one-pot process}

The present invention relates to a nanobrush-type environmentally friendly alternative plasticizer compound and its preparation method using a single reactor process.

Phthalate plasticizers account for 92% of the global plasticizer market (Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248 Note) As an additive used to give flexibility, durability, cold resistance, etc. to polyvinyl chloride (hereinafter referred to as PVC), and to improve processability by lowering the viscosity during melting, it is added to PVC in various contents to give solid pipes From hard products to soft and stretchable soft products that can be used for food packaging, blood bags, and flooring, they are more closely related to real life than any other materials and are widely used for direct contact with the human body.

However, despite the compatibility with PVC of phthalate-based plasticizers and excellent softening properties, the recent use of PVC products containing phthalate-based plasticizers has gradually leaked out of the product, leading to the estimation of endocrine disruptor (environmental hormone) substances and heavy metals. Hazardous controversy has been raised that it can act as a carcinogen (NR Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2008, 42, 7522-7527). In particular, in the 1990s, after the release of the report that diethylhexyl phthalate (DEHP), which is the most used phthalate plasticizer in the United States in the 1960s, was released, With increasing interest in environmental hormones, global environmental regulations have begun, including various studies on the human hazards of phthalate plasticizers.

To this end, many researchers have developed new non-phthalate-based plasticizers that exclude phthalic anhydride used in the manufacture of phthalate-based plasticizers or suppressed phthalate-based plasticizers in order to respond to environmental hormone problems and environmental regulations caused by phthalate-based plasticizer spills. The company is conducting research to develop a spill prevention technology that can significantly reduce risks and meet environmental standards.

In the existing non-phthalate-based alternative plasticizer research, Korean Patent Laid-Open Publication No. 2004-0057792 prepared soft polyvinyl chloride using an aliphatic polyester compound having a molded structure. When the molded aliphatic polyester compound is used as a PVC plasticizer, there is no possibility of leakage and it is known that it can impart excellent ductility. However, the terminal hydroxyl groups of the molded aliphatic polyester compounds are well known to backbiting carbonyl groups of the main chain to decompose polyester compounds or promote hydrolysis (DM Bigg "Polylactide Copolymer). : Effect of Copolymer Ratio and End Capping on Their Properties "Advances in Polymer Technology 2005, 24, 69-82). In addition, in order to prepare a molded aliphatic polyester compound, a step of precipitating with cold methanol and then filtering is required. The use of a large amount of organic solvent is a concern for environmental pollution, such as economic burden and waste water, it is known that there is a problem in the economic efficiency as the process, such as precipitation, filtration, washing, drying is lengthened substantially. As a result, polyvinyl chloride produced using a molded aliphatic polyester compound is easily decomposed and discolored by heat, and lacks economical efficiency, commercial viability and environmental friendliness.

Korea Patent Publication 2004-0057792 (2004.07.02)

 Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248  N. R. Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2008, 42, 7522-7527  D. M. Bigg "Polylactide Copolymer: Effect of Copolymer Ratio and End Capping on Their Properties" Advances in Polymer Technology 2005, 24, 69-82

Therefore, the technical problem to be achieved by the present invention is a plasticizer used in the production of PVC, having a sufficiently large molecular weight and excellent compatibility with PVC having excellent physical properties such as heat-blocking resistance and excellent softness, as well as heat resistance and light resistance. It is to manufacture nano brush type eco-friendly alternative plasticizer. In addition, the step of eliminating the precipitation and filtration using an organic solvent and simplifying the manufacturing process in a single reactor process, to provide a manufacturing method of nano-brush type eco-friendly alternative plasticizer with economical, commercial and eco-friendly.

In order to achieve the above technical problem, the present invention provides a nanobrush-type eco-friendly alternative plasticizer represented by the following formula (1) and a method for manufacturing the same:

[Formula 1]

In Formula 1,

A is a linear aliphatic polyol represented by Formula A-1, a cyclic aliphatic polyol represented by Formula A-2, a linear aliphatic polyol containing an oxygen atom represented by Formula A-3, and Residues other than -OH in a polyol selected from the group consisting of cyclic aliphatic polyols containing an oxygen atom represented;

[Formula A-1]

C _n R ₁ R ₂ . R _{2n +2}

In Formula A-1, C _n is a linear aliphatic central carbon atom, n is an integer of 1 or more, and R ₁ to R _{2n +2} are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P _e is shown as a, b, c, d and e is an integer of 0 or more each of a + b + c + d + e is 1 or more, the R ₁ ~ R _{2n + 2} is 2 or more of the c _m H _{As 2m} OH, m is an integer of at least 0;

[Formula A-2]

C _n R ₁ R ₂ . R _2n

In Formula A-2, C _n is a cyclic aliphatic central carbon atom, n is an integer of 3 or more, and R ₁ to R _2n are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P represented by _e, and a, b, c, d and e are as a + b + c + d + e is 1 or more, the R 2 or more is c _m H _2m OH of _2n as an integer of 0 or more, respectively, m is An integer of at least 0;

[Formula A-3]

C _n O _f R ₁ R ₂ . R _{2n +2}

In Formula A-3, C _n is a linear aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, and R ₁ to R _{2n +2} are bonded to a central carbon atom Are independently of each other represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more and a + b + c + d + e is 1 or more, and R _At least two of ₁ to R _{2n +2} are C _m H _2m OH, wherein m is an integer of at least 0;

[A-4]

C _n O _f R ₁ R ₂ . R _2n

In Formula A-4, C _n is a cyclic aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, n + f is an integer of 3 or more, and R ₁ ~ R _2n is a mutually independent substituent bonded to a central carbon atom and is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is at least 1, at least two of R ₁ to R _2n are C _m H _2m OH, m is an integer of 0 or more;

R is represented by hydrogen or C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of at least 0 and a + b + c + d + e is at least 1;

R 'is alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 3 to 10 carbon atoms;

w is 0 or 1;

x is an integer of 1 or more;

y is an integer of 1 or more;

z is the number of -OH of the polyol of A, and is an integer of 2 or more.

The brush length (repeating unit) of the nanobrush-type eco-friendly alternative plasticizer according to the present invention means a y value in which the unit of -C (= O)-(CHR) _x -O- in Chemical Formula 1 is repeated, y Is an integer of 1 or more, but preferably an integer of 1 to 50 . In addition, x in Chemical Formula 1 is an integer of 1 or more, but preferably an integer of 1 to 10. In addition, the number average molecular weight of the nanobrush-type eco-friendly alternative plasticizer of the formula (1) according to the present invention is 300 to 35,000, the longer the brush length has the characteristics of linear polymers such as chain entanglement does not play a role as a plasticizer with high plasticization efficiency I can't.

Nanobrush-type eco-friendly alternative plasticizer according to the present invention may be exemplified by the following structure, but is not limited thereto.

In addition, the present invention is a linear aliphatic polyol represented by the formula (A-1), a cyclic aliphatic polyol represented by the formula (A-2), a linear aliphatic polyol containing an oxygen atom represented by the formula (A-3) and a formula (A) Ring-opening polymerization of a lactone monomer represented by the following formula (2) with a brush material, using a polyol selected from the group consisting of cyclic aliphatic polyols containing an oxygen atom represented by -4 as a core material, Finally, by end-capping the terminal hydroxyl group of the brush, the present invention relates to a method for preparing a nanobrush-type environmentally friendly plasticizer of the formula:

[Formula A-1]

C _n R ₁ R ₂ . R _{2n +2}

In Formula A-1, C _n is a linear aliphatic central carbon atom, n is an integer of 1 or more, and R ₁ to R _{2n +2} are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P _e is shown as a, b, c, d and e is an integer of 0 or more each of a + b + c + d + e is 1 or more, the R ₁ ~ R _{2n + 2} is 2 or more of the c _m H _{As 2m} OH, m is an integer of at least 0;

[Formula A-2]

C _n R ₁ R ₂ . R _2n

In Formula A-2, C _n is a cyclic aliphatic central carbon atom, n is an integer of 3 or more, and R ₁ to R _2n are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P represented by _e, and a, b, c, d and e are as a + b + c + d + e is 1 or more, the R 2 or more is c _m H _2m OH of _2n as an integer of 0 or more, respectively, m is An integer of at least 0;

[Formula A-3]

C _n O _f R ₁ R ₂ . R _{2n +2}

In Formula A-3, C _n is a linear aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, and R ₁ to R _{2n +2} are bonded to a central carbon atom Are independently of each other represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more and a + b + c + d + e is 1 or more, and R _At least two of ₁ to R _{2n +2} are C _m H _2m OH, wherein m is an integer of at least 0;

[A-4]

C _n O _f R ₁ R ₂ . R _2n

In Formula A-4, C _n is a cyclic aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, n + f is an integer of 3 or more, and R ₁ ~ R _2n is a mutually independent substituent bonded to a central carbon atom and is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is at least 1, at least two of R ₁ to R _2n are C _m H _2m OH, m is an integer of 0 or more;

[Formula 2]

In Formula 2, x is an integer of 1 or more and R is hydrogen or a substituent bonded to one or more carbon atoms constituting the ring is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each As an integer of 0 or more, a + b + c + d + e is 1 or more. In Formula 2, x is an integer of 1 or more, but preferably an integer of 1 to 10.

Acid, acid halides, anhydrides, isocyanates and the like are used in stabilizing terminal hydroxyl groups after the ring-opening polymerization, and are specifically selected from compounds of the following structures:

R'C (= O) OH

R'C (= O) X

R'C (= O) OC (= O) R '

R'-NCO

R 'is alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 3 to 10 carbon atoms; X is halogen.

Acetic acid, propionic acid butyric acid, acetyl chloride, propionyl chloride, butyryl chloride, acetic anhydride, propionic anhydride, butyric anhydride, methyl isocyanate, ethyl isocyanate, propyl isocyanate, cyclo for stabilization of terminal hydroxyl groups after ring-opening polymerization Hexanecarboxylic acid, cyclohexyl acetic acid, and the like can be used, but most preferably acetic anhydride is used.

Acetic anhydride (Ac ₂ O) was used in the embodiment of the present invention in stabilizing terminal hydroxyl groups.

Hereinafter, a linear or cyclic aliphatic polyol core material containing a large number of hydroxyl groups constituting the nanobrush-type eco-friendly alternative plasticizer of the present invention, for the stabilization of the lactone-based monomer brush material and the brush terminal hydroxyl group by ring-opening polymerization of such a core material hydroxyl group A substance is explained in full detail, for example.

In the material for manufacturing the nanobrush-type eco-friendly alternative plasticizer of the present invention, the linear aliphatic polyol core material represented by Chemical Formula A-1 may be represented by the following Chemical Formula a (when n = 1) and b (when n = 2): And c (when n = 3), a linear aliphatic polyol core material containing an oxygen atom represented by Formula A-3 is represented by the following Formula d (when n = 2, f = 1), The cyclic aliphatic polyol core material containing the oxygen atom represented by Chemical Formula A-4 is represented by the following Chemical Formula e (when n = 5 and f = 1).

In Formulas a, b, c, d and e, R ₁ to R ₈ are each independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms and cyclo having 3 to 10 carbon atoms. Alkyl or C _m H _2m OH, m is an integer of 0 or more, and in each formula is included at least two C _m H _2m OH.

As such, since the polyol core materials of Formulas a, b, c, d, and e may have several to several tens or more hydroxyl groups, the number of brushes of the nanobrush-type eco-friendly alternative plasticizer may be determined according to the selection of the core material.

In the material for the manufacture of the nanobrush-type eco-friendly alternative plasticizer of the present invention, the lactone monomer brush material of the formula (2) which is ring-opened and bonded to the hydroxyl group of the polyol core material is represented by the following formula (3) It forms a main chain, and such lactone monomer brush material is β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, tridecanolactone, pentadecanolactone, γ-penta Decanolactone and γ-valerolactone, and derivatives in which the hydrogen present in these monomers is substituted with R in Formula 2:

(3)

In Formula 3, R is represented by hydrogen or C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more and a + b + c + d + e is 1 or more. ; It is preferable that x is an integer of 1 or more as an integer of 1 or more; It is preferable that y is an integer of 1-50 as an integer of 1 or more.

At this time, the brush length of the nanobrush-type eco-friendly alternative plasticizer can be adjusted through the molar ratio of the brush material to the hydroxyl group of the core material.

In the material for manufacturing the nanobrush-type eco-friendly alternative plasticizer of the present invention, in order to stabilize the brush terminal hydroxyl group, a material having a functional group such as an acid, an acid halide, an anhydride, and an isocyanate capable of reacting with a hydroxyl group is used. The ring-opening polymerization reaction is terminated through hydroxyl stabilization, giving heat plasticity and light resistance to plasticized PVC as a nanobrush-type eco-friendly alternative plasticizer. In addition, it prevents side reactions and decomposition reactions such as transesterification due to terminal hydroxyl groups accelerated at 80 ° C. or higher, and unreacted substances can be removed at 80 to 200 ° C. under reduced pressure.

Specifically, the manufacturing method of the nanobrush-type eco-friendly alternative plasticizer according to the present invention is as follows. The core material and the brush material are put in one reactor and the ring-opening polymerization reaction is carried out by bulk polymerization which does not require a solvent. At this time, the molar ratio for adjusting the number of brushes and the length of the brush is determined according to each hydroxyl group reactivity in the core material, and the type and amount of the catalyst for ring-opening polymerization of the brush material, the reaction temperature and the reaction time are comprehensive and complex. Consider. Thereafter, a substance capable of reacting with the terminal hydroxyl group of the brush is added and the terminal hydroxyl group is stabilized. In this case, the material for stabilizing terminal hydroxyl groups is also selected as a material that can proceed without solvent in consideration of reactivity and economical efficiency. After the completion of all the reaction, the final product is nanobrush-type eco-friendly alternative plasticizer by removing the unreacted product at 80 to 200 ℃ without the step of precipitation, filtration, washing, drying using a solvent.

Through this manufacturing method, it has a sufficiently large molecular weight and excellent compatibility with PVC to prevent leakage to the outside, excellent softness, heat resistance and light resistance not easily decomposed or discolored by heat, and a single reactor process without using an organic solvent. By simplifying the manufacturing process, it is possible to manufacture nanobrush-type eco-friendly alternative plasticizers that are economical, commercial and eco-friendly.

As such, the nanobrush-type eco-friendly alternative plasticizer of the present invention can be very usefully used as a plasticizer of PVC, and the polyvinyl chloride composition includes 5 to 150 parts by weight of the nanobrush-type eco-friendly alternative plasticizer in 100 parts by weight of polyvinyl chloride. Can be done.

The nanobrush-type eco-friendly alternative plasticizer prepared by the manufacturing method according to the present invention uses a harmless core material and environmentally friendly and biocompatible brush material to exclude phthalate compounds which are endocrine disruptors. Possessing a large number of carbonyl groups, which have a molecular weight and can interact strongly with the PVC chain, it has good miscibility with PVC and bonding ability to prevent leakage to the outside of the PVC. In addition, nano brush-type eco-friendly alternative plasticizers have a three-dimensional conformation, and compared to general linear structures of the same molecular weight, the brush length of each unit is short, which eliminates chain entanglement, and is excellent in PVC due to its small hydrodynamic volume and excellent chain motion. Give the surname And from the stabilization of the brush terminal hydroxyl group, the nanobrush-type eco-friendly alternative plasticizer has heat resistance and light resistance that are not easily decomposed or discolored by heat. In addition, in the manufacturing method of the nanobrush-type eco-friendly alternative plasticizer, it is possible to manufacture nanobrush-type eco-friendly alternative plasticizer with economical, commercial and eco-friendly by simplifying the manufacturing process in a single reactor process without using an organic solvent. Therefore, by using the nanobrush-type eco-friendly plasticizer of the present invention, it is possible to respond to environmental hormone problems and environmental regulations while at the same time giving excellent plasticization effect to PVC by replacing all existing plasticizers.

1 is an infrared spectroscopy (FT-IR) result of the compound prepared in Example 2 and Comparative Preparation Example 1.
Figure 2 is a hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) results of the compound prepared in Example 2 and Comparative Preparation Example 1.
3 is a mass spectrometry (MALDI-TOF) result of the compound prepared in Example 2 and Comparative Preparation Example 1. FIG.
4 is an ultraviolet / visible (UV / Vis.) Spectroscopic analysis result of the PVC film prepared according to Example 4 and Comparative Example 2.
Figure 5 is a differential scanning calorimetry (DSC) analysis of the PVC film prepared according to Example 4 and Comparative Examples 1 and 2.
6 is a tensile test result of the PVC film prepared according to Example 4 and Comparative Examples 1 and 2.
7 is a solvent extractability evaluation results of the PVC film prepared according to Example 4 and Comparative Example 2.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

( Nano brush type  Eco-friendly alternative plasticizer manufacturing)

≪ Example 1 >

In this embodiment, as one of the linear aliphatic polyol core materials represented by Chemical Formula a, trimethylolpropane (TMP) having three hydroxyl groups is used as the core material and epsilon-caprolactone having 6 carbon atoms as the lactone monomer. ( ε -caprolactone, CL) is an example of manufacturing nano brush type eco-friendly alternative plasticizer using brush material.

22.83 g (0.2 mol) of CL, the brush material, was added to the three-necked flask, and the molar ratio of the brush material to the hydroxyl group of the TMP, the core material, was 1: 5 to adjust the brush length. (0.01 mol) and put in an oil bath (temperature controlled to 120 ℃). After stirring in an argon atmosphere, the solid core material is completely dissolved in the liquid brush material, and then drops of drops of stannous octoate (Sn (Oct) ₂ ) are subjected to ring-opening polymerization for 24 hours. After the polymerization was completed, the temperature of the oil bath was adjusted to 60 ° C., and 6.13 g (0.06 mol) of acetic anhydride (Ac ₂ O) was added to react for 6 hours to stabilize the terminal hydroxyl group. Finally, the oil bath was adjusted to 100 ° C. and decompressed by a vacuum pump to remove unreacted materials. A nanobrush-type eco-friendly alternative plasticizer using TMP as a core material was prepared.

The nanobrush-type eco-friendly alternative plasticizer prepared through this process was subjected to infrared spectroscopy (FT-IR), hydrogen magnetic resonance spectroscopy ( ¹ H-NMR) and high resolution matrix assisted laser desorption mass spectrometry (MALDI-TOF). It was confirmed whether the nano brush-type eco-friendly alternative plasticizer synthesis having the desired brush length and molecular weight. The experimental results are shown in Table 1 below.

<Example 2>

Instead of TMP, which is the core material used in Example 1, as one of the linear aliphatic polyol core materials containing a non-carbon atom represented by Chemical Formula d, dipentaerythritol (DPTOL) having six hydroxyl groups is used as the core material. Except for using as, the same method as in Example 1 to prepare a nano brush-type eco-friendly alternative plasticizer made of DPTOL as a core material, and also confirmed the synthesis by the same method. The experimental results are shown in Table 1 below.

<Example 3>

Instead of TMP, which is the core material used in Example 1, as one of the cyclic aliphatic polyol core materials containing a non-carbon atom represented by Chemical Formula e, methyl-alpha-D-glucoside having four hydroxyl groups (methyl- Except for using α-D-glucopyranoside (MG) as a core material, a nanobrush-type eco-friendly alternative plasticizer was prepared in the same manner as in Example 1, and the synthesis was confirmed in the same manner. The experimental results are shown in Table 1 below.

Example core Brush can Brush length
(repeating unit) Number average molecular weight
(g / mol) One TMP 3 5.5 1800 2 DPTOL 6 4.8 3400 3 MG 4 8.9 2400

Brush length in Table 1 is an average value calculated by the integral ratio of NMR.

Comparative Preparation Example 1 Preparation of DPTOL Core Polyester Compound Not Terminally Stabilized

In the same manner as in Example 1, except that acetic anhydride added for terminal hydroxyl stabilization in Example 1 was used, and instead of TMP, which is a core material, dipentaerythritol (DPTOL) was used as the core material. A terminally unstabilized DPTOL core polyester compound was prepared.

Infrared spectroscopy (FT-IR) to confirm the terminal stabilization [FIG. 1], hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) was confirmed the chemical structure [FIG. 2], mass spectrometry (MALDI) -TOF) to confirm the side reaction (decomposition) [Fig. 3]. Although the two compounds appear to be successfully polymerized from FIG. 1 and FIG. 2, the mass spectrometry using the MALDI-TOF of FIG. 3 shows the peaks of the linear polyester compound and the cyclic polyester compound caused by side reactions. .

( Nano brush type  As an eco-friendly alternative plasticizer Plasticized  Polyvinyl chloride)

<Example 4>

This embodiment is to produce a soft PVC film by solution blending using the nano brush-type eco-friendly alternative plasticizer prepared in Examples 1, 2 and 3 and a commercial PVC resin (Hanhwa Chemical Co., Ltd., P-1000) It is an example.

50 ml of tetrahydrofuran (THF) is prepared as a solvent of solution blending in a beaker, and 3 g of a commercial PVC resin is dissolved. Here, based on a commercial PVC resin, 60 phr (part per hundred resin) of the nanobrush-type eco-friendly alternative plasticizer prepared by the method of Examples 1, 2, and 3 was dissolved, and a heat stabilizer (Songwon Industry, MT-800 ) 2 phr was dissolved to form a clear solution. The transparent solution thus obtained was poured into a chalet and evaporated at 50 ° C. for 24 hours to prepare a transparent soft PVC film plasticized with a nanobrush-type eco-friendly alternative plasticizer in which THF solvent was completely removed.

&Lt; Comparative Example 1 &

This comparative example is an example of manufacturing a PVC film containing no plasticizer.

Without using the nanobrush-type eco-friendly alternative plasticizer used in Example 4, a transparent PVC film containing no plasticizer was prepared in the same manner as in Example 4.

Comparative Example 2

This comparative example is an example of manufacturing a soft PVC film using DEHP, one of the general-purpose phthalate-based plasticizers used previously.

A transparent soft PVC film was prepared in the same manner as in Example 4, except that DEHP, which is one of general-purpose phthalate-based plasticizers, was used instead of the nanobrush-type eco-friendly alternative plasticizer used in Example 4.

[ Experimental Example  One] Nano brush type  As an eco-friendly alternative plasticizer Plasticized  Evaluation of Optical Properties of Polyvinyl Chloride

This example is an example for evaluating the optical properties of the flexible PVC film prepared in Example 4.

In order to evaluate the optical properties of the produced soft PVC film, the transmittance of the soft PVC film prepared in Example 4 was measured at a wavelength of 650 nm, which is visible light region, by using UV / Vis. Spectroscopy. (FIG. 4). Referring to Figure 4, the produced soft PVC has a transmittance of more than 85%, it was confirmed that has a transmittance similar to the soft PVC prepared in Comparative Example 2.

[ Experimental Example  2] Nano brush type  As an eco-friendly alternative plasticizer Plasticized  Polyvinyl chloride Plasticization  Efficiency evaluation

This example is an example for evaluating the plasticization efficiency of the flexible PVC film prepared in Example 4.

In order to evaluate the plasticization efficiency of the produced soft PVC film, the temperature increase rate of the flexible PVC film prepared in Example 4 in the temperature range of -110 ~ 140 ℃ under nitrogen stream by using differential scanning calorimetry (DSC) analysis 10 ℃ / The glass transition temperature was measured by fixing in minutes (FIG. 5). Referring to FIG. 5, the glass transition temperature of the manufactured soft PVC is significantly lower than the glass transition temperature of the PVC film containing no plasticizer prepared in Comparative Example 1, and the differential scanning calorimetry curve with PVC It was confirmed that the glass transition temperature of the plasticizer did not appear, but a single glass transition temperature appeared. This shows that both PVC and plasticizers have excellent compatibility with each other, and that the nano-brush-type eco-friendly alternative plasticizer has a fast molecular motion between the PVC chains, making the PVC chains flexible and plasticized. In addition, when the plasticization efficiency is calculated using Equation 1 compared to the glass transition temperature of the soft PVC prepared in Comparative Example 2, it was confirmed that it has a high plasticization efficiency of more than 80% (Table 2). From this, it was confirmed that the nanobrush-type eco-friendly alternative plasticizer has excellent plasticization efficiency along with excellent compatibility with PVC.

[Formula 1]

division Glass transition temperature (캜) Plasticization efficiency (%) Example 4 PVC / TMP Core (Example 1) －19.1 97.0 PVC / DPTOL Core (Example 2) －7.8 86.5 PVC / MG core (Example 3) －4.9 83.8 Comparative Example 1 neat PVC 84.8 ? Comparative Example 2 PVC / DEHP －22.3 100.0

[ Experimental Example  3] Nano brush type  As an eco-friendly alternative plasticizer Plasticized  Evaluation of Mechanical Properties of Polyvinyl Chloride

This example is an example for evaluating the mechanical properties of the flexible PVC film prepared in Example 4.

In order to evaluate the mechanical properties of the manufactured soft PVC film, the soft PVC film prepared in Example 4 was subjected to stress and strain using a universal testing machine (UTM) according to ASTM D628-08 “Standard Test Method for Tensile Properties of Plastics”. It was measured (FIG. 6). Referring to FIG. 6, the stress-strain curve of the manufactured soft PVC is soft without any yield point similar to that of the soft PVC prepared in Comparative Example 2, unlike the PVC containing no plasticizer prepared in Comparative Example 1. It was confirmed that the curve having the characteristics of the material is shown.

[ Experimental Example  4] Nano brush type  As an eco-friendly alternative plasticizer Plasticized  Polyvinyl chloride Outflow  evaluation

In this embodiment, in order to compare and evaluate that the plasticizer is transferred to the external solvent phase and outflow when using a PVC product, the solvent extractability of the soft PVC film prepared in Example 4 and the soft PVC film prepared in Comparative Example 2 It is an example for evaluation.

In order to evaluate the solvent extractability of the manufactured soft PVC film, the flexible PVC film prepared in Example 4 and the flexible PVC film prepared in Comparative Example 2 were prepared using ASTM D5227-01 “Standard Test Method for Measurement of Hexane Extractable Content of Polyolefins. Test was conducted. Specifically, the resulting soft PVC film was left to stir for 1 hour at 50 ° C. of normal hexane (n-hexane) for 2 hours, and the soft PVC film was taken out and dried sufficiently at room temperature for at least 12 hours, and then the weight before and after the test was measured. The flow rate of the plasticizer was quantitatively evaluated by measuring the following equation (2). Referring to FIG. 7, in the case of the soft PVC film prepared in Comparative Example 2, 80% or more of the used plasticizer was extracted with the normal hexane solvent, whereas in the case of the soft PVC film prepared in Example 4, the normal PVC solvent was extracted. It was confirmed that there was no plasticizer at all.

[Formula 2]

Claims (10)

Nanobrush-type eco-friendly alternative plasticizer represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
A is a linear aliphatic polyol represented by Formula A-1, a cyclic aliphatic polyol represented by Formula A-2, a linear aliphatic polyol containing an oxygen atom represented by Formula A-3, and Residues other than -OH in a polyol selected from the group consisting of cyclic aliphatic polyols containing an oxygen atom represented;
[Formula A-1]
C _n R ₁ R ₂ . R _{2n +2}
In Formula A-1, C _n is a linear aliphatic central carbon atom, n is an integer of 1 or more, and R ₁ to R _{2n +2} are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P _e is shown as a, b, c, d and e is an integer of 0 or more each of a + b + c + d + e is 1 or more, the R ₁ ~ R _{2n + 2} is 2 or more of the c _m H _{As 2m} OH, m is an integer of at least 0;
[Formula A-2]
C _n R ₁ R ₂ . R _2n
In Formula A-2, C _n is a cyclic aliphatic central carbon atom, n is an integer of 3 or more, and R ₁ to R _2n are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P represented by _e, and a, b, c, d and e are as a + b + c + d + e is 1 or more, the R 2 or more is c _m H _2m OH of _2n as an integer of 0 or more, respectively, m is An integer of at least 0;
[Formula A-3]
C _n O _f R ₁ R ₂ . R _{2n +2}
In Formula A-3, C _n is a linear aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, and R ₁ to R _{2n +2} are bonded to a central carbon atom Are independently of each other represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more and a + b + c + d + e is 1 or more, and R _At least two of ₁ to R _{2n +2} are C _m H _2m OH, wherein m is an integer of at least 0;
[Formula A-4]
C _n O _f R ₁ R ₂ . R _2n
In Formula A-4, C _n is a cyclic aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, n + f is an integer of 3 or more, and R ₁ ~ R _2n is a mutually independent substituent bonded to a central carbon atom and is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is at least 1, at least two of R ₁ to R _2n are C _m H _2m OH, m is an integer of 0 or more;
R is represented by hydrogen or C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of at least 0 and a + b + c + d + e is at least 1;
R 'is alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 3 to 10 carbon atoms;
w is 0 or 1;
x is an integer of 1 or more;
y is an integer of 1 or more;
z is the number of -OH of the polyol of A, and is an integer of 2 or more.
The method of claim 1,
Nanobrush-type eco-friendly alternative plasticizer is a nanobrush-type eco-friendly alternative plasticizer having a number average molecular weight of 300 to 35,000.
The method of claim 1,
The nanobrush-type eco-friendly alternative plasticizer nanobrush-type eco-friendly alternative plasticizer selected from the following compounds;

,

, or

.
The linear aliphatic polyol represented by the formula (A-1), the cyclic aliphatic polyol represented by the formula (A-2), the linear aliphatic polyol containing the oxygen atom represented by the formula (A-3), and the formula (A-4) The nanobrush-type eco-friendly alternative plasticizer of claim 1 by ring-opening polymerization of a polyol core material selected from the group consisting of cyclic aliphatic polyols containing an oxygen atom and a lactone monomer represented by Formula 2 and stabilizing terminal hydroxyl groups How to manufacture:
[Formula A-1]
C _n R ₁ R ₂ . R _{2n +2}
In Formula A-1, C _n is a linear aliphatic central carbon atom, n is an integer of 1 or more, and R ₁ to R _{2n +2} are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P _e is shown as a, b, c, d and e is an integer of 0 or more each of a + b + c + d + e is 1 or more, the R ₁ ~ R _{2n + 2} is 2 or more of the c _m H _{As 2m} OH, m is an integer of at least 0;
[Formula A-2]
C _n R ₁ R ₂ . R _2n
In Formula A-2, C _n is a cyclic aliphatic central carbon atom, n is an integer of 3 or more, and R ₁ to R _2n are mutually independent substituents bonded to the central carbon atom, and C _a H _b O _c N _d P represented by _e, and a, b, c, d and e are as a + b + c + d + e is 1 or more, the R 2 or more is c _m H _2m OH of _2n as an integer of 0 or more, respectively, m is An integer of at least 0;
[Formula A-3]
C _n O _f R ₁ R ₂ . R _{2n +2}
In Formula A-3, C _n is a linear aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, and R ₁ to R _{2n +2} are bonded to a central carbon atom Are independently of each other represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more and a + b + c + d + e is 1 or more, and R _At least two of ₁ to R _{2n +2} are C _m H _2m OH, wherein m is an integer of at least 0;
[Formula A-4]
C _n O _f R ₁ R ₂ . R _2n
In Formula A-4, C _n is a cyclic aliphatic central carbon atom containing at least one oxygen atom, n is an integer of 1 or more, f is an integer of 1 or more, n + f is an integer of 3 or more, and R ₁ ~ R _2n is a mutually independent substituent bonded to a central carbon atom and is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is at least 1, at least two of R ₁ to R _2n are C _m H _2m OH, m is an integer of 0 or more;
R is represented by hydrogen or C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of at least 0 and a + b + c + d + e is at least 1;
(2)

In Formula 2, x is an integer of 1 or more and R is hydrogen or a substituent bonded to one or more carbon atoms constituting the ring is represented by C _a H _b O _c N _d P _e and a, b, c, d and e are each As an integer of 0 or more, a + b + c + d + e is 1 or more.
The method of claim 4, wherein
The lactone-based monomer brush material of Formula 2 is a method for producing a nano-brush type eco-friendly plasticizer, characterized in that to form a main chain represented by the formula (3):
(3)

In Formula 3, R is represented by hydrogen or C _a H _b O _c N _d P _e and a, b, c, d and e are each an integer of 0 or more; x is an integer of 1 or more; y is an integer of 1 or more.
The method of claim 4, wherein
Method for preparing a nano-brush type eco-friendly plasticizer, characterized in that for adding the acid, acid halide, anhydride or isocyanate selected from the following to stabilize the terminal hydroxyl group after the ring-opening polymerization:
R'C (= O) OH
R'C (= O) X
R'C (= O) OC (= O) R '
R'-NCO
R 'is alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 3 to 10 carbon atoms; X is halogen.
The method according to claim 6,
As the stabilizer, acetic acid, butyric acid butyrate, acetyl chloride, propionyl chloride, butyryl chloride, acetic anhydride, propionic anhydride, butyrate anhydride, methyl isocyanate, ethyl isocyanate, propyl isocyanate, cyclohexanecarboxylic acid or cyclohexyl acetic acid are used. Method of manufacturing a nanobrush-type eco-friendly alternative plasticizer, characterized in that.
The method of claim 4, wherein
Method for producing a nano-brush type eco-friendly alternative plasticizer comprising the step of removing the unreacted material by reducing the pressure at 80 to 200 ℃.
A polyvinyl chloride composition comprising the nanobrush-type eco-friendly alternative plasticizer according to any one of claims 1 to 3.
The method of claim 9,
The nanobrush-type eco-friendly alternative plasticizer 5 to 150 parts by weight based on 100 parts by weight of polyvinyl chloride composition.

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