KR101282556B1 - Plasticizer composition and method for preparing the same - Google Patents

Abstract

상기 R1은 탄소수 1~12 알킬이며, R2는 탄소수 1~12 알킬이며, R3은 탄소수 1~12 알킬이며, n은 1 내지 5인 정수이다.
[화학식 2]

상기 R4~R6는 각각 탄소수 1~12 알킬이며, R7~R9는 각각 탄소수 1~12 알킬이며 n1~n3은 각각 0~5인 정수이다. 단, n1~n3 중 적어도 하나는 1이다.The present invention relates to a plasticizer composition comprising a compound represented by the following Chemical Formula 1 containing a 1,2,4-trioxolane ring, a method for preparing the same, and a vinyl chloride resin composition comprising the plasticizer composition.
[Formula 1]

R1 is C1-C12 alkyl, R2 is C1-C12 alkyl, R3 is C1-C12 alkyl, n is an integer of 1-5.
(2)

R4 to R6 are each alkyl having 1 to 12 carbons, R7 to R9 are each alkyl having 1 to 12 carbons, and each of n1 to n3 is an integer of 0 to 5, respectively. Provided that at least one of n1 to n3 is 1;

Description

Plasticizer composition and preparation method thereof {Plasticizer composition and method for preparing the same}

The present invention relates to an environmentally friendly plasticizer composition, a method for preparing the same, and a vinyl chloride resin composition including the plasticizer composition.

The polyvinyl chloride resin is a homopolymer of vinyl chloride or an interpolymer containing 50% or more of vinyl chloride. It is a general-purpose resin that can be used by a process such as extrusion molding, injection molding and calendering. Through such processing, It is used extensively as a material for various products ranging from wires, electromechanical products, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging materials and medical supplies. Such a polyvinyl chloride resin can be added with various additives such as a plasticizer, a stabilizer, a filler, and a pigment to impart various properties to the resin.

Among the above additives, the plasticizer is added to polyvinyl chloride resin and is an essential additive for imparting various physical properties and functions such as processability, flexibility, electrical insulation and adhesiveness.

In the case of plasticizers, low volatility is a very important factor, which is important both during incorporation into plastic compositions and during actual use of molded products. In addition, the plasticizers provided for application in the food and beverage sector and in the pharmaceutical sector should be harmless to health. Representative types of such plasticizers include phthalates.

However, due to the debate on regenerative toxicity under the legal system already regulating toxic substances, the use of phthalates is expected to decrease significantly in the future. Therefore, there is a demand for the development of a plasticizer having a plasticization efficiency equivalent to that of a phthalate-based plasticizer while using a substance containing no phthalate as a basic skeleton.

Recently, the company is focusing on developing plasticizers using environmentally-friendly compounds derived from nature. Eco-friendly plasticizers by epoxidation of soybean oil, rapeseed oil, sunflower oil and fatty acid esters are studied. This is due to the unique thermal stability due to the presence of the mono-oxolane ring by epoxidation as well as the eco-friendly cotton derived from natural materials. Although the plasticizing effect was also shown to be sufficient, there is a fatal disadvantage that the leaching of the plasticizer occurs when exposed to heat treatment and UV for a long time, resulting in a sticky surface. This is because of the incompleteness of the epoxidation, the unreacted material is separated from the double bond.

Plasticizers in plastics enhance the plasticity of the polymer chains by forming secondary bonds between the polymer and the plasticizers and breaking the primary bonds between the polymer chains. The biggest problem in the commercialization of these plasticizers is the leaching and desorption of plasticizers during polymer heat treatment, and the most important consideration to solve this problem is the introduction of the polar portion in the plasticizer, which plays an important role in the formation of the secondary bond between the polymer and the plasticizer.

Accordingly, the present inventors have introduced a polar group to a plasticizer using an environmentally-friendly nature-derived compound to develop a plasticizer composition having excellent thermal and mechanical properties.

The present invention is to provide a plasticizer composition, a method for preparing the same and a vinyl chloride resin composition comprising the plasticizer composition.

The present invention provides a plasticizer composition comprising a compound represented by the following formula (1) or (2) containing a 1,2,4-trioxolane ring.

 [Formula 1]

R1 is C1-C12 alkyl, R2 is C1-C12 alkyl, R3 is C1-C12 alkyl, n is an integer of 1-5.

[Formula 2]

R4 to R6 are each alkyl having 1 to 12 carbons, R7 to R9 are each alkyl having 1 to 12 carbons, and each of n1 to n3 is an integer of 0 to 5, respectively. Provided that at least one of n1 to n3 is 1;

In addition, the present invention comprises the steps of passing ozone to the oil or fatty acid ester; It provides a method for producing a plasticizer composition containing 1,2,4-trioxolane (trioxolane) ring comprising a.

The present invention also provides a vinyl chloride resin composition comprising the plasticizer composition.

The plasticizer composition according to the present invention is environmentally friendly as a non-phthalate system, and when the vinyl chloride resin of the present invention including the plasticizer composition is prepared, excellent products in terms of hardness (plasticization efficiency), thermal stability, and mechanical properties can be obtained. In addition, the plasticizer composition may be used as an antimicrobial agent and additive in food, cosmetics, pharmaceutical industry and the like.

1A is a saturated fatty acid ester, B is a 1,2,4-trioxolane formation structure diagram (B) in unsaturated fatty acid ester.
Figure 2 shows a conventional phthalate plasticizer structure diagram.
Figure 3 shows a structural formula that the environmentally friendly plasticizer is bonded through the internal polymerization as an internal plasticizer in PVC.

In the present invention, the plasticizer is a substance added to the resin to lower the melting temperature and melt viscosity of the resin to facilitate molding processing. In general, linear polymers have a hard and inflexible state due to the disruption of polymer chain movement due to attraction between molecular chains. Therefore, in order to give flexibility to the resin, the intermolecular bonds must be weakened or broken. A plasticizer plays such a role.

In the present invention, by forming a polar group 1,2,4-trioxolane ring in the oil and fatty acid ester, to provide a plasticizer composition with significantly improved thermal stability and polarity.

More specifically, the present invention provides a plasticizer composition comprising a compound represented by Formula 1 or Formula 2 below containing a 1,2,4-trioxolane ring in one aspect.

[Formula 1]

R1 is C1-C12 alkyl, R2 is C1-C12 alkyl, R3 is C1-C12 alkyl, n is an integer of 1-5.

[Formula 2]

R4 to R6 are each alkyl having 1 to 12 carbons, R7 to R9 are each alkyl having 1 to 12 carbons, and each of n1 to n3 is an integer of 0 to 5, respectively. Provided that at least one of n1 to n3 is 1;

The compound containing 1,2,4-trioxolane or ozonide ring refers to a compound in which an 1,2,4-trioxolane ring is formed as a polar group in an oil or fatty acid ester.

That is, there is no double bond in the oil or fatty acid ester and 1,2,4-trioxolane is formed. In order to form the 1,2,4-trioxolane ring, ozone in oil or fatty acid ester may be permeated.

The oil is not limited thereto, but may include vegetable oils, animal oils and waste cooking oils, may include unsaturated fatty acids, and may include triester groups.

The fatty acid ester may be a fatty acid ester derived from vegetable oil, animal oil and waste cooking oil. That is, it may be a fatty acid ester produced by transesterification of the oil, or an unsaturated fatty acid ester.

More specifically, the fatty acid ester is a substance produced by the reaction between the fatty acid and the alcohol. For example, when the alcohol is methanol, the reaction thereof is shown in Scheme 1 below.

[Reaction Scheme 1]

The fatty acid may include an unsaturated fatty acid having one or more double bonds. This is by passing ozone through the unsaturated fatty acid ester produced by the reaction of the unsaturated fatty acid and alcohol, thereby eliminating the double bond and forming a 1,2,4-trioxolane ring.

The formation of 1,2,4-trioxolane can be analyzed using 1H NMR, 13C NMR, and FTIR. In one embodiment of the present invention, the double bond of unsaturated fatty acids was reduced and the effective production of 1,2,4-trioxolane, the desired polar moiety, was seen (Table 2).

The present invention can be used as an alternative to existing phthalate-based plasticizers by using environmentally friendly natural-derived compounds such as vegetable oils, animal oils and waste cooking oils and fatty acid esters produced by transesterification thereof.

In order to be a plasticizer for each type of oil and fatty acid ester, the content may be 3 to 20% based on the molecular weight of the 1,2,4-trioxolane ring.

Also, in another aspect of the present invention, passing ozone through an oil or fatty acid ester; It provides a method for producing a plasticizer composition containing 1,2,4-trioxolane (trioxolane) ring comprising a. More specifically, by using a microbubble device to pass a micro ozone bubble through the oil or fatty acid ester, to utilize a 100% ozone to prepare a plasticizer composition containing a 1,2,4-trioxolane ring.

As described above, in order to be a plasticizer for each type of oil and fatty acid ester, the content may be 3 to 20% based on the molecular weight of 1,2,4-trioxolane ring, which is the concentration of ozone and ozone. By adjusting the contact time (2 minutes to 10 minutes) of the content of oxolane can be adjusted.

1,2,4-trioxolane in oil or fatty acid esters by passing the ozone at a rate of 0.5-1 l / min, preferably 30 g-50 O ₃ / m ³ ozone at a rate of 0.5 l / min. ) The content of the ring can be adjusted.

In another aspect of the present invention, a vinyl chloride resin (PVC) composition comprising the plasticizer composition is provided.

The molecular chain of PVC is polarized by the electronegativity of chlorine, and it has weak electrostatic bond between molecular chains by this polarity. Heating PVC during the forming process of soft PVC weakens the bonds between the molecular chains and increases the spacing. When plasticizer molecules penetrate this chain, the electrostatic attraction between the polarization of the molecular chain and the polarization of the plasticizer is fixed by the electrostatic attraction and remains in place after cooling, preventing the access of the PVC molecular chain, and the micro brown of the PVC molecular chain. It enables exercise and gives PVC flexibility.

The vinyl chloride resin composition according to the present invention has excellent heat loss, migration resistance, hardness, elongation, and tensile strength. In addition, it has a number of excellent properties, in particular, can solve many problems that may occur when using a general-purpose plasticizer. In general, the general plasticizer has a problem that a considerable amount is transferred to the outside after being processed with the resin, whereas the plasticizer applied to the vinyl chloride resin composition according to the present invention has the advantage of complementing the plasticizer transition and fragile properties As a result, the problem of external transition can be solved, and thus, the problem of contaminating the surrounding plasticizer does not occur.

The vinyl chloride resin composition may include 2 to 100 parts by weight of the plasticizer composition of the present invention based on 100 parts by weight of vinyl chloride resin.

If the content of the plasticizer composition is less than 2 parts by weight, there is a problem in that it does not have properties such as plasticization efficiency and adhesiveness, and if it is more than 100 parts by weight, there is a problem of inferior thermal stability and migration resistance.

The plasticizer composition according to the present invention is not limited to polyvinyl chloride, and may contain chlorine-containing resins such as chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-ethylene copolymer. Chlorine-containing resins such as vinyl chloride-propylene copolymers, vinyl chloride-styrene copolymers, vinyl chloride-isobutylene copolymers, vinyl chloride-vinylidene chloride copolymers, and vinyl chloride-vinyl ether copolymers, and their mutual Blended products, also blended products with chlorine-containing resins and chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene terpolymers, ethylene-vinyl acetate copolymers, polyesters, and the like It can also be applied to block copolymers and graft copolymers.

The plasticizer composition according to the present invention may be appropriately increased or decreased depending on the use of the resin composition. However, when added to less than 2 parts by weight, the plasticizer composition may not achieve flexibility or processability that may be expressed by the plasticizer, and exceeds 100 parts by weight. In the case of addition by addition, it is not preferable to secure necessary mechanical properties and possibly elute.

Meanwhile, the method for preparing the polyvinyl chloride resin is not particularly limited and may be prepared by methods well known in the art.

The polyvinyl chloride resin of the present invention containing the plasticizer composition according to the present invention includes building materials such as wall finishing materials, flooring materials, window frames and wallpaper; Wire covering materials; Interior and exterior materials for automobiles; Agricultural materials such as houses and tunnels; Food packaging materials such as fish such as wraps and trays; Film forming agents such as underbody sealants, plastisols, paints, and inks; Synthetic leather, coated fabrics, hoses, pipes, sheets, baby toys, glove, and the like can be used in, but not limited to.

The present invention also provides a cosmetic composition comprising the plasticizer composition.

The plasticizer composition may include 2 to 100 parts by weight of the plasticizer composition based on 100 parts by weight of the total cosmetic composition.

Cosmetic compositions according to the invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. These are all formulations suitable for topical application, for example emulsions, suspensions, microemulsions, microcapsules, microgranules or ionic (liposomes) obtained by dispersing an oil phase in solutions, gels, solids, pasty anhydrous products, aqueous phases and It may be provided in the form of a nonionic vesicle dispersant or in the form of a cream, skin, lotion, powder, ointment, spray or cone stick. It can also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions may be prepared according to conventional methods in the art.

In addition, the cosmetic composition according to the present invention is a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softener, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant, water, an ionic type or a non- With ionic emulsifiers, fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or any other ingredients commonly used in cosmetics. It may contain adjuvants commonly used in the same cosmetic or dermatology field. Such adjuvants are introduced in amounts commonly used in the cosmetics or dermatological fields.

In addition, the cosmetic composition comprising the plasticizer composition of the present invention, may be provided for use in basic cosmetics, makeup cosmetics, body cosmetics, scalp cosmetics or shaving cosmetics.

Examples of the basic cosmetics include creams, lotions, packs, massage creams, emulsions, etc. The makeup cosmetics include foundation, makeup base, lipstick, eyeshadow, eyeliner, mascara, eyebrow pencil, and the like. Examples include soaps, liquid cleansers, baths, massage agents, sunscreen creams and sun oils, and cosmetics for scalp include hair tonics and scalp treatments, and aftershave and shaving creams. Etc.

The present invention also provides a food composition comprising the plasticizer composition.

The plasticizer composition may include 2 to 100 parts by weight of the plasticizer composition based on 100 parts by weight of the total food composition.

The food composition of the present invention may be provided in the form of a food, in particular a functional food composition. The functional food composition of the present invention includes ingredients that are commonly added during food preparation, and include, for example, proteins, carbohydrates, fats, nutrients and seasonings. For example, when prepared with a drink, a flavoring agent or natural carbohydrate may be included as an additional component in addition to the chiacremonone compound as an active ingredient.

For example, natural carbohydrates include monosaccharides (e.g., glucose, fructose, etc.); Disaccharides (e.g., maltose, sucrose, etc.); oligosaccharide; Polysaccharides (e.g., dextrin, cyclodextrin and the like); And sugar alcohols (e.g., xylitol, sorbitol, erythritol, etc.). As the flavoring agent, natural flavoring agents (e.g., taumartin, stevia extract, etc.) and synthetic flavoring agents (e.g., saccharin, aspartame, etc.) can be used.

In addition, the food composition according to the present invention can be prepared in the form of a mixture by mixing with a known active ingredient known to be effective in enhancing exercise performance, fatigue recovery or stress relief, functional food (functional food), nutritional supplements (nutritional) It includes all forms such as supplements, health foods and food additives. Food compositions of this type may be prepared in a variety of forms according to conventional methods known in the art. For example, the health food can be prepared in the form of tea, juice and drink containing grape root extract, and can be ingested by granulating, encapsulating or powdering a food composition containing the grape root extract as an active ingredient.

The kind of the food composition is not particularly limited. Examples of the food to which the substance may be added include dairy products including meat, sausage, bread, chocolate, candy, snacks, confectionery, noodles, gum, ice cream, various soups, beverages, teas, drinks, alcoholic beverages and vitamin complexes. And the like, but not limited to all of the health foods in the conventional sense.

In addition, 1-5 wt% of the plasticizer composition of the present invention may be mixed with biodiesel to be used as a biodiesel low temperature flow improver, and 2-100 wt% of the plasticizer composition of the present invention may be used as cutting oil.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are intended to illustrate the contents of the present invention, but the scope of the present invention is not limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

< Example  1>

1. Preparation of plasticizer composition

The bubble column was prepared by filling 50 ml of various oils or fatty acid esters and passing 40 g O 3 / m 3 ozone at a rate of 0.5 l / min. The inflow and outflow ozone concentrations were measured at 10 minute intervals using a TOA OZ-30 ozone meter, and after ozonation, purged with nitrogen gas to remove unreacted ozone.

Table 1 shows the fatty acid distribution table by vegetable oil type. Ozonation proceeded up to 0.20 gO3 / ml for SFO and 0.18 gO3 / ml for SBO and RSO, and 0.06 gO3 / ml for total PMO due to less unsaturated components. . The 1,2,4-trioxalane rings produced through ozonation of each oil were identified using FTIR.

Fatty acid distribution table by vegetable oil type Vegetable oil Fatty acid composition (%) 16: 0 18: 0 18: 1 18: 2 18: 3 SFO 6 3 17 74 0 SBO 12 3 23 55 6 PMO * 45 4 40 10 RSO 3 One 64 22 8

* 14: 0 contains about 1%

The disappearance of double bonds and formation of 1,2,4-triol sol in various ozonated oils and fatty acid esters was analyzed using 1 H NMR and 13 C NMR. The results are shown in Table 2. Double bonds of unsaturated fatty acids were reduced and effective production of 1,2,4-trioxolane, the desired polar moiety, was observed.

Percent Unsaturated Fatty Acid Composition and 1,2,4-trioxolane Formation after Vegetable Oil Ozonation Unsaturated fatty acid Soybean oil Soybean oil after 7 hours ozonation C18: 1 Oleic acid 24 18 C18: 2 Linoleic acid 54 39.4 C 18: 3 Linolenic acid 7 4.48 1,2,4-trioxolane 0 13.5 Aldehyde 0 0

2. Vinyl chloride resin  Composition manufacturing

Specimens were prepared to evaluate the performance of the plasticizer. That is, 70 parts by weight of a plasticizer composition including the compound of Formula 1 as a plasticizer and 100 parts by weight of polyvinyl chloride resin (LG Chem, product name LS-100) as a plasticizer, and 1 part by weight of Korea Daehyup LFX-1100 as a stabilizer, In the figure, a 1 mm preheating, 1.5 min pressurization, and 2 min cooling was performed to make a 2 mm sheet, and various dumbbell specimens were prepared.

The specimens prepared in Example 1 were subjected to the following test, and the results are summarized in Table 3 below.

The tensile strength

Tensile strength was measured by pulling the cross head speed to 200 mm / min using a test instrument UTM (manufacturer; Instron, Model Name; 4466) by the ASTM D638 method. (kgf / mm 2) = Load value (kgf) / thickness (mm) x width (mm) was calculated.

Elongation

According to ASTM D638 method, after pulling the crosshead speed to 200 mm / min using the UTM, measuring the point where the specimen is cut, elongation (%) = length after extension / initial length × Calculated as 100.

Hardness

Hardness was measured as an indicator of plasticization efficiency, and the hardness of the hardness tester (A type) (manufacturer; Toyoseiki, model name; C-751400101) was completely lowered to one part of the specimen based on ASTM D2240. The values were read and five sites were tested for each specimen and then averaged. The hardness was measured once immediately after preparing the specimen, and once again after one day after the specimen was prepared.

Heating loss

The composition was operated at 165 ° C. for 3 minutes using a roll mill to produce 0.8 mm thick sheets, and then 60 g of this composition was used for 10 minutes at 185 ° C. using a roll mill to produce 0.4 mm. Specimens were prepared in thickness. Then, after 24 hours, the weight of the specimen was measured, and calculated as heating loss (% by weight) = 1-(weight after 10 minutes of working at 185 ° C) / 60 g × 100.

Inner planet

Performance resistance was measured for each specimen prepared above to the initial weight (Wi) to 4 decimal places and put a sheet (3 cm × 3 cm) between the ABS resin plate in an oven at 70 ℃, and then a load of 1 kg After leaving for 72 hours in the state of addition, the specimen was taken out and stored in a thermostat for 4 hours or more, the weight (Wo) of the specimen was measured, and then calculated as the transfer amount (% by weight) = (Wi-Wo) / Wi × 100. .

< Comparative example  1>

Specimens were prepared in the same manner as in Example 1, using the most widely used di-2-ethylhexylphthalate (DOP) as a plasticizer. Tests were carried out in the same manner as in Example 1 with the prepared specimens and the results are summarized in Table 3 below.

< Comparative example  2>

Di-2-ethylhexyl phthalate A specimen was prepared in the same manner as in Example 1 using di-2-ethylhexyl adipate, which has been widely used as a plasticizer. Tests were carried out in the same manner as in Example 1 with the prepared specimens and the results are summarized in Table 3 below.

Metrics Example Comparative Example 1 Comparative Example 2 Hardness (shore A) 84.5 80 78 Tensile strength (kgf / cm2) 185 160 150 Elongation (%) 416 440 460 Heat loss (%) 0.25 0.94 5 Solubility Factor (-) 8.8 8.9 8.6 Migratory resistance (%) 0.48 1.15 1.3

From the results of Table 3, Example 1, which is a plasticizer of the present invention, has the same or higher plasticization efficiency as compared to Comparative Examples 1 and 2, which are the most common plasticizers, as well as other physical properties, such as heating loss. It can be seen that it is above the level.

Hardness is closely related to plasticization efficiency, and the fact that the hardness is not significantly increased is important because it means that compatibility with the resin was maintained. In addition, the process is accompanied by a high temperature treatment, the heating loss is expected to be less fume generation.

Therefore, the plasticizer composition of the present invention is excellent in plasticizing efficiency, more suitable for a variety of molding according to various uses and can be expected to use a variety of.

Claims (6)

Plasticizer composition comprising a compound represented by the following formula (1) or (2) containing a 1,2,4-trioxolane ring.
[Formula 1]

R1 is C1-C12 alkyl, R2 is C1-C12 alkyl, R3 is C1-C12 alkyl, n is an integer of 1-5.
(2)

R4 to R6 are each alkyl having 1 to 12 carbons, R7 to R9 are each alkyl having 1 to 12 carbons, and each of n1 to n3 is an integer of 0 to 5, respectively. Provided that at least one of n1 to n3 is 1; The plasticizer composition according to claim 1, wherein the 1,2,4-trioxolane ring content is 3 to 20 wt% based on molecular weight. Passing ozone through an oil or fatty acid ester selected from the group consisting of vegetable oils, animal oils and waste cooking oils; Method for producing a plasticizer composition containing 1,2,4-trioxolane (trioxolane) ring comprising a. The method for producing a plasticizer composition according to claim 3, wherein 30 g to 50 O ₃ / m ³ ozone is passed at a rate of 0.5 to 1 l / min. A vinyl chloride resin composition comprising the plasticizer composition according to claim 1. The vinyl chloride resin composition according to claim 5, comprising 70 parts by weight of the plasticizer composition based on 100 parts by weight of the vinyl chloride resin.

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