WO2012121553A2 - Composé plastifiant alternatif de type nanobrosse écologique et procédé permettant de fabriquer ce composé au moyen d'une synthèse monotope - Google Patents

Composé plastifiant alternatif de type nanobrosse écologique et procédé permettant de fabriquer ce composé au moyen d'une synthèse monotope Download PDF

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WO2012121553A2
WO2012121553A2 PCT/KR2012/001699 KR2012001699W WO2012121553A2 WO 2012121553 A2 WO2012121553 A2 WO 2012121553A2 KR 2012001699 W KR2012001699 W KR 2012001699W WO 2012121553 A2 WO2012121553 A2 WO 2012121553A2
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integer
formula
represented
nanobrush
carbon atom
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PCT/KR2012/001699
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Korean (ko)
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WO2012121553A3 (fr
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곽승엽
최우혁
윤경준
최경재
최영균
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서울대학교산학협력단
한화케미칼 주식회사
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Priority claimed from KR1020120023979A external-priority patent/KR101354141B1/ko
Publication of WO2012121553A2 publication Critical patent/WO2012121553A2/fr
Publication of WO2012121553A3 publication Critical patent/WO2012121553A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • 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)
  • PVC polyvinyl chloride
  • PVC polyvinyl chloride
  • 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.
  • Korean Patent Laid-Open Publication No. 2004-0057792 prepared soft polyvinyl chloride using an aliphatic polyester compound having a molded structure.
  • 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.
  • 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).
  • 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.
  • the present invention provides a nanobrush-type eco-friendly alternative plasticizer represented by the following formula (1) and a method for manufacturing the same:
  • 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;
  • C n is a linear aliphatic central carbon atom
  • n is an integer of 1 or more
  • R 1 to R 2n + 2 are mutually independent substituents bonded to the central carbon atom
  • C a H b O c N d expressed as P e and 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 or more of the 2, c m H As 2m OH, m is an integer of at least 0;
  • C n is a cyclic aliphatic central carbon atom
  • n is an integer of 3 or more
  • R 1 to R 2n are mutually independent substituents bonded to the central carbon atom
  • 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 0 or greater;
  • 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
  • R 1 to R 2n + 2 are bonded to a central carbon atom
  • 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;
  • 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
  • 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.
  • x in Chemical Formula 1 is an integer of 1 or more, but preferably an integer of 1 to 10.
  • 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 You will not.
  • Nanobrush-type eco-friendly alternative plasticizer according to the present invention may be exemplified by the following structure, but is not limited thereto.
  • 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:
  • C n is a linear aliphatic central carbon atom
  • n is an integer of 1 or more
  • R 1 to R 2n + 2 are mutually independent substituents bonded to the central carbon atom
  • C a H b O c N d expressed as P e and 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 or more of the 2, c m H As 2m OH, m is an integer of at least 0;
  • C n is a cyclic aliphatic central carbon atom
  • n is an integer of 3 or more
  • R 1 to R 2n are mutually independent substituents bonded to the central carbon atom
  • 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 0 or greater;
  • 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
  • R 1 to R 2n + 2 are bonded to a central carbon atom
  • 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;
  • 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
  • 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;
  • 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.
  • 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 ' 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.
  • 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.
  • 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.
  • 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.
  • the number of brushes of the nanobrush-type eco-friendly alternative plasticizer may be determined according to the selection of the core material.
  • 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 ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, tridecanolactone, pentadecanolactone, ⁇ -penta Decanolactone and ⁇ -valerolactone, and derivatives in which the hydrogen present in these monomers is substituted with R in Formula 2:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a substance capable of reacting with the terminal hydroxyl group of the brush is added and the terminal hydroxyl group is stabilized.
  • 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.
  • the final product is nanobrush-type eco-friendly alternative plasticizer by removing the unreacted product at 80 to 200 °C without the step of precipitation, filtration, washing, drying using a solvent.
  • this manufacturing method 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.
  • nanobrush-type eco-friendly alternative plasticizers that are economical, commercial and eco-friendly.
  • 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.
  • 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.
  • the nanobrush-type eco-friendly alternative plasticizer has heat resistance and light resistance that are not easily decomposed or discolored by heat.
  • 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.
  • Example 1 is an infrared spectroscopy (FT-IR) result of the compound prepared in Example 2 and Comparative Preparation Example 1.
  • FT-IR infrared spectroscopy
  • 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.
  • FIG. 3 is a mass spectrometry (MALDI-TOF) result of the compound prepared in Example 2 and Comparative Preparation Example 1.
  • MALDI-TOF mass spectrometry
  • Example 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.
  • TMP trimethylolpropane
  • epsilon-caprolactone having 6 carbon atoms
  • CL ⁇ -caprolactone
  • the nanobrush-type eco-friendly alternative plasticizer produced 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.
  • FT-IR infrared spectroscopy
  • 1 H-NMR hydrogen magnetic resonance spectroscopy
  • MALDI-TOF high resolution matrix assisted laser desorption mass spectrometry
  • TMP which is the core material used in Example 1
  • DPTOL dipentaerythritol
  • Table 1 The experimental results are shown in Table 1 below.
  • TMP which is the core material used in Example 1
  • methyl-alpha-D-glucoside having four hydroxyl groups methyl- Except for using ⁇ -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.
  • Table 1 The experimental results are shown in Table 1 below.
  • Example core Brush can Brushing 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.
  • Example 2 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.
  • TMP which is a core material
  • DPTOL dipentaerythritol
  • 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.
  • tetrahydrofuran 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.
  • THF tetrahydrofuran
  • 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 stii 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.
  • This comparative example is an example of manufacturing a PVC film containing no plasticizer.
  • Example 4 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.
  • 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.
  • This example is an example for evaluating the optical properties of the flexible PVC film prepared in Example 4.
  • 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).
  • 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.
  • This example is an example for evaluating the plasticization efficiency of the flexible PVC film prepared in Example 4.
  • the glass transition temperature was measured by fixing in minutes (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.
  • 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
  • This example is an example for evaluating the mechanical properties of the flexible PVC film prepared in Example 4.
  • 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).
  • UTM universal testing machine
  • ASTM D628-08 Standard Test Method for Tensile Properties of Plastics
  • 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.
  • 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.
  • 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.
  • 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.
  • the nanobrush-type eco-friendly alternative plasticizer has heat resistance and light resistance that are not easily decomposed or discolored by heat.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un composé plastifiant alternatif de type nanobrosse écologique et un procédé permettant de fabriquer ce composé au moyen d'une synthèse monotope. Un plastifiant alternatif de type nanobrosse selon la présente invention consiste en un composé dans lequel un monomère de lactone biocompatible écologique subit une polymérisation par ouverture de cycle avec une substance principale, qui n'est dangereuse ni pour le corps ni pour l'environnement afin d'éliminer un phtalate, une substance bloquant le système endocrinien, et enfin dans lequel un groupe hydroxyle se trouvant à l'extrémité d'une brosse est stabilisé. Le plastifiant alternatif de type nanobrosse écologique présente un effet plastifiant supérieur et il peut permettre de répondre aux problèmes liés aux hormones environnementales et aux régulations environnementales, en raison d'une miscibilité supérieure avec le PVC et de l'absence de fuite à l'extérieur du PVC. En outre, le procédé de fabrication de ce plastifiant consiste en la synthèse monotope sans sans solvant organique, ce qui permet de fabriquer un plastifiant alternatif de type nanobrosse écologique ayant une viabilité environnementale, économique et commerciale.
PCT/KR2012/001699 2011-03-08 2012-03-08 Composé plastifiant alternatif de type nanobrosse écologique et procédé permettant de fabriquer ce composé au moyen d'une synthèse monotope WO2012121553A2 (fr)

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Application Number Priority Date Filing Date Title
KR20110020339 2011-03-08
KR10-2011-0020339 2011-03-08
KR1020120023979A KR101354141B1 (ko) 2011-03-08 2012-03-08 나노브러쉬형 친환경 대체가소제 화합물 및 단일반응기 공정을 이용한 이의 제조방법
KR10-2012-0023979 2012-03-08

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Cited By (1)

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CN105153576A (zh) * 2015-08-21 2015-12-16 飞佛特种纺织品（宁波）有限公司 一种生物基环保阳光面料涂层配方

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KR100365721B1 (ko) * 2000-12-07 2002-12-27 (주)에코테크 폴리염화비닐 가소제용 고차구조제어형 지방족폴리에스테르 화합물 및 이를 포함하는 폴리염화비닐 블렌드
KR20080060752A (ko) * 2006-12-27 2008-07-02 주식회사 엘지화학 가소제 조성물, 이의 제조방법 및 이를 포함하는 자동차전선 테이프용 염화비닐 수지 조성물

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CN105153576A (zh) * 2015-08-21 2015-12-16 飞佛特种纺织品（宁波）有限公司 一种生物基环保阳光面料涂层配方

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