CN103788406A - Biological environment-friendly plasticizer capable of completely replacing dioctyl-phthalate (DOP) - Google Patents
Biological environment-friendly plasticizer capable of completely replacing dioctyl-phthalate (DOP) Download PDFInfo
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Abstract
The invention belongs to the technical field of a novel material, and particularly relates to a biological environment-friendly plasticizer capable of completely replacing dioctyl-phthalate (DOP). The plasticizer is prepared from the following ingredients by mass percent in a mixing manner: 15-50% of epoxy vegetable oil, 10-50% of epoxidized fatty acid methyl ester, 0-50% of epoxy fatty acid polyol ester, and the balance of cold resistant plasticizer. The biological environment-friendly plasticizer is reasonable in formula, low in cost, low in melting temperature, and strong in weather fastness, all production raw materials are from renewable resources, and cheap and available, the production cost can be saved, the capacity is greatly improved, the product can be completely biodegraded, and the biological environment-friendly plasticizer is free of poison and harm to the environment, and can certainly replace the traditional DOP plasticizer on the market in the future.
Description
Technical field
The present invention relates to a kind of bio-based environment-friendly plasticizer that can substitute DOP completely, belong to new material technology field.
Background technology
Softening agent is the industrial macromolecular material auxiliary agent being widely used, and is one of additives for plastics of world wide production and consumption maximum, adds this material in plastic working, can make its snappiness strengthen, easily processing.Softening agent has again dividing of primary plasticizer and extender plasticizer.If the amorphous domain that plasticizer molecule only can insertion polymerization thing, this softening agent is non-solvent type plasticizer, namely so-called extender plasticizer.If the amorphous domain that plasticizer molecule can not only insertion polymerization thing can be inserted again crystal region simultaneously, this softening agent is solvent-type plasticizer, i.e. so-called primary plasticizer.Approximately 7,500,000 tons/year of the global softening agent aggregated capacity power to 2012, global softening agent ultimate production is 5,900,000 tons/year, its Middle and North America accounts for 22%, the Asian-Pacific area accounts for 38%, Europe accounts for 25%, other areas account for 15%.PVC is the maximum user of softening agent, accounts for 95% of the total consumption of global softening agent, at North America proportion also a little higher than 90%.On softening agent market, widely used primary plasticizer, substantially take phthalate materials such as DOP as main, accounts for 69% of ultimate production.
Phthalic ester plasticizer is classified as doubtful Environmental Hormone, its bio-toxicity mainly belongs to oestrogenic hormon and androgen antagonist activity, can cause endocrine disturbance, encumber organism Reproductive Performance, comprise that reproduction rate reduction, miscarriage, born defect, abnormal sperm count, cover ball damage, and also can cause malignant tumour, cause teratogenesis.The effect of plasticizer DOP is similar to artificial hormone, can endanger male reproductive function and impel female precocious puberty, and long-term huge uptake can cause liver cancer.Because child is in the endocrine system Development of Reproductive System phase, the potential hazard that DOP brings child can be larger:
1, may cause the entanglement of child's sex, comprise sexual organ shorten little, sex character is not obvious;
Though 2, whether carcinogenicly cannot confirm the mankind at present, can produce carcinogenic reaction to animal;
3, phthalic ester may affect hormone secretion in fetus and infants, causes hormonal imbalance, causes children's sexual precocity.
Biology department of Hong Kong Baptist University is studied with guinea pig, finds the mouse of once taking " fluidizer ", and the offspring under birth is take female as main, and can affect it and ovulate normally; Even if birth is lower male, its reproductive organ compared with normal little by 2/3rds, and sperm quantity also subtracts greatly, reflection " softening agent " toxicity belongs to androgen antagonist activity, causes endocrine disturbance.Expert says, research can be applied to it the mankind, shows that to clisis for a long time " softening agent " large compared with women to male influence.
In October, 2012, according to Britain's " Daily Mail " recently, American Studies personnel find, contact the women of a large amount of above-mentioned article, and the time entering into the climacteric period shifts to an earlier date nearly two-and-a-half years than other women.And these chemical substances may also can cause some women 15 years menelipsis ahead of time.
In view of the poisonous and harmful effect of phthalic easter plastizer to environment and the unsustainable property of raw material sources, substitute products are all being fallen over each other to research and develop in countries in the world, to stop as soon as possible as early as possible the use of phthalic easter plastizer.
Epoxy soybean oil and epoxy aliphatic acid methyl ester are as first-generation bio-based softening agent, and brisk buying and selling for existing market.But the consistency of epoxy soybean oil and epoxy aliphatic acid methyl ester and PVC has problem, addition exceedes 10% and just there will be the problem such as oil impregnate, frosting, affect the quality of plastic prod and use function, thereby can only be used as extender plasticizer, cannot substitute phthalic ester plasticizer completely.
The consistency of citric acid three ester class softening agent and PVC is fine, can be used as primary plasticizer and realize completely alternative to phthalic ester plasticizer, but output is limited, can not meet so huge market requirement, and production cost is higher, in price, cannot contend with phthalic ester plasticizer.
Summary of the invention
The present invention has invented a kind of bio-based environment-friendly plasticizer that can substitute DOP completely.Comparatively unique, it has invented a kind of softening agent being made up of organism-based raw material completely, can realize the object that substitutes phthalic ester type softening agent with renewable resources raw material completely.Operate according to the present invention, can be under the prerequisite of production cost that does not increase existing PVC plastics, realize completely alternative to phthalic ester type softening agent such as DOP of green non-poisonous environment-friendly type softening agent.This is vital for thoroughly banning use of early Phthalates for the softening agent of the toxic effect of environment.
Specifically, first, we find that the epoxyfatty acid polyol esters such as epoxidation tetramethylolmethane four oleic acid esters have good compatible property with PVC, and can arbitrary proportion miscible with the cold resisting type softening agent such as citric acid three ester class bio-based softening agent, form the PVC primary plasticizer that plasticizing effect is good, high temperature performance is excellent.Establish thus the basis that can substitute the bio-based environment-friendly plasticizer of DOP completely.
Secondly, we find that the epoxyfatty acid polyol esters such as epoxidation tetramethylolmethane four oleic acid esters are the solubilizing agent of the epoxy plasticisers such as a kind of effective epoxy soybean oil, epoxy aliphatic acid methyl ester class, can effectively improve the consistency of epoxy plasticiser and polyvinyl chloride resin, avoid separating out of epoxy plasticiser, its addition is greatly increased, thereby the interpolation cost of softening agent is maintained in the existing level of DOP.
We find, this softening agent can be mixed and be formed by the composition of following weight percent: epoxyfatty acid polyol ester 15～50%; Epoxidized vegetable oil 10～50%; Epoxy aliphatic acid methyl ester 5～50%; Cold resisting type softening agent surplus.Epoxidized vegetable oil wherein can be epoxy soybean oil, can be also epoxidised Oleum Gossypii semen, rapeseed oil, Semen Maydis oil, peanut oil, sunflower seed oil, safflower oil, or the mixture being made up of them.Epoxy aliphatic acid methyl ester wherein refers to take fatty acid methyl ester as raw material, the product obtaining after the art breading identical with the epoxidation of soybean oil.Fatty acid methyl ester can be soya fatty acid methyl esters, also can be Witconol 2301, methyl linoleate, Linolenic acid methylester, cotton oil fatty acid methyl ester, corn oil fatty acid methyl esters, rapeseed oil fatty acid methyl esters, peanut oil fatty acid methyl esters, sunflower seed oil fatty acid methyl ester, safflower oil fatty acid methyl ester, or the mixture being formed by them.Epoxyfatty acid polyol ester wherein refers to take polyhydric alcohol fatty acid ester as raw material, the product obtaining after the art breading identical with the epoxidation of soybean oil.Polyol esters of fatty acids refers to take polyvalent alcohol and lipid acid as raw material, the product obtaining after esterification.Described polyvalent alcohol can be ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, also can be propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, tetramethylolmethane, dipentaerythritol, tripentaerythritol, TriMethylolPropane(TMP), ditrimethylolpropane, three TriMethylolPropane(TMP)s, glucose, maltose, sucrose, lactose, sorbyl alcohol, N.F,USP MANNITOL, maltose alcohol, or the mixture being formed by them.Described lipid acid can be soya fatty acid, also can be oleic acid, linolic acid, linolenic acid, cotton oil lipid acid, corn oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid, sunflower seed oil lipid acid, safflower oil lipid acid, or the mixture being formed by them.Cold resisting type softening agent wherein can be triethyl citrate, also can be acetyl triethyl citrate, butyryl triethyl citrate, oleoyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, butyryl tributyl citrate, oleoyl tributyl citrate, trioctyl lemon acid, ATOC, butyryl trioctyl lemon acid, oleoyl trioctyl lemon acid, Octyl adipate, dioctyl terephthalate, citric acid tri-n-hexyl ester, ATHC, butyryl citric acid tri-n-hexyl ester, oleoyl citric acid tri-n-hexyl ester, or the mixture being formed by them.
Embodiment
Example below will illustrate working method of the present invention, but can not serve as limitation of the invention.
Example one
With epoxy soybean oil, epoxy soybean fatty acid methyl ester, epoxy tetramethylolmethane four oleic acid esters and tributyl acetylcitrate are raw material, according to the allotment of proportioning shown in table 1 softening agent, after then mixing with polyvinyl chloride resin, take DOP as contrast, carry out performance test, test result is in table 2.Temperature when T50% is wherein softening agent weightless 50%, T50% more high thermal stability is better.Plasticization effect and with PVC consistency all take DOP as reference sample.
Table 1
Table 1 (Continued)
Table 1 (Continued)
Table 2
| Formula | T 50％(℃) | With PVC consistency | Flash-point (℃) | Zero pour (℃) | Plasticization effect |
| DOP | 237 | - | ≥217 | -60 | - |
| 1 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 2 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 3 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 4 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 5 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 6 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 7 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
Table 2 (Continued)
| Formula | T 50％(℃) | With PVC consistency | Flash-point (℃) | Zero pour (℃) | Plasticization effect |
| 8 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 9 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 10 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 11 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 12 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 13 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 14 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 15 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 16 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 17 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 18 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 19 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 20 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 21 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 22 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 23 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 24 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 25 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 26 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 27 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 28 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 29 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 30 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 31 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 32 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 33 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 34 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 35 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 36 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 37 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 38 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 39 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 40 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 41 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 42 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 43 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 44 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 45 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 46 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 47 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 48 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 49 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 50 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 51 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 52 | ≥350 | Suitable with DOP | ≥200 | ≤0 | Suitable with DOP |
| 53 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 54 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 55 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 56 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
Table 2 (Continued)
Table 2 (Continued)
| Formula | T 50％(℃) | With PVC consistency | Flash-point (℃) | Zero pour (℃) | Plasticization effect |
| 106 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 107 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 108 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 109 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 110 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 111 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
| 112 | ≥350 | Suitable with DOP | ≥200 | ≤-20 | Suitable with DOP |
Can find out from the result of test, the plasticization effect of softening agent of the present invention and all suitable with DOP with PVC consistency, and thermostability is obviously better than DOP, though flash-point and zero pour are slightly poorer than DOP, but reach acceptable level, can substitute DOP and use as softening agent.Example two
With epoxy soybean oil, epoxy soybean fatty acid methyl ester, epoxy tetramethylolmethane four soybean fat acid esters and dioctyl terephthalate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with dioctyl terephthalate with epoxy tetramethylolmethane four soybean fat acid esters, gained formula also alternative DOP uses as softening agent.
Example three
With epoxy cottonseed oil, epoxy cotton oil fatty acid methyl ester, epoxy tetramethylolmethane four cotton oil fatty acid esters and tributyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy cottonseed oil, substitute epoxy soya fatty acid methyl esters with epoxy cotton oil fatty acid methyl ester, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with tributyl citrate with epoxy tetramethylolmethane four cotton oil fatty acid esters, gained formula also alternative DOP uses as softening agent.
Example four
With epoxy rapeseed oil, epoxy rapeseed oil fatty acid methyl ester, epoxy dipentaerythritol four oleic acid esters and butyryl tributyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy rapeseed oil, substitute epoxy soya fatty acid methyl esters with epoxy rapeseed oil fatty acid methyl ester, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with butyryl tributyl citrate with epoxy dipentaerythritol four oleic acid esters, gained formula also alternative DOP uses as softening agent.
Example five
With epoxy Semen Maydis oil, epoxy corn oil fatty acid methyl esters, ethylene oxide glycol four corn oil fatty acid esters and oleoyl tributyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy Semen Maydis oil, substitute epoxy soya fatty acid methyl esters with epoxy corn oil fatty acid methyl esters, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with oleoyl tributyl citrate with ethylene oxide glycol four corn oil fatty acid esters, gained formula also alternative DOP uses as softening agent.
Example six
With epoxy peanut oil, epoxy peanut oil fatty acid methyl esters, epoxy propylene glycol four peanut oil fatty acid esters and triethyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy peanut oil, substitute epoxy soya fatty acid methyl esters with epoxy peanut oil fatty acid methyl esters, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with triethyl citrate with epoxy propylene glycol four peanut oil fatty acid esters, gained formula also alternative DOP uses as softening agent.
Example seven
With epoxy sunflower seed oil, epoxy sunflower seed oil fatty acid methyl ester, epoxy trimethylolpropane tris sunflower seed oil fatty acid ester and acetyl triethyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy sunflower seed oil, substitute epoxy soya fatty acid methyl esters with epoxy sunflower seed oil fatty acid methyl ester, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with acetyl triethyl citrate with epoxy trimethylolpropane tris sunflower seed oil fatty acid ester, gained formula also alternative DOP uses as softening agent.
Example eight
With epoxy safflower oil, epoxy safflower oil fatty acid methyl ester, epoxy sucrose eight safflower oil fatty acid esters and butyryl triethyl citrate are raw material, operate according to the experimental technique identical with example 1, have obtained the result similar to example 1.Show to substitute epoxy soybean oil with epoxy safflower oil, substitute epoxy soya fatty acid methyl esters with epoxy safflower oil fatty acid methyl ester, substitute tetramethylolmethane four oleic acid esters, substitute after tributyl acetylcitrate with oleoyl triethyl citrate with epoxy sucrose eight safflower oil fatty acid esters, gained formula also alternative DOP uses as softening agent.
Claims (9)
1. one kind can substitute the bio-based environment-friendly plasticizer of DOP completely.This softening agent is mixed and is formed by the composition of following weight percent:
1) epoxyfatty acid polyol ester 15～50%;
2) epoxidized vegetable oil 10～50%;
3) epoxy aliphatic acid methyl ester 5～50%;
4) cold resisting type softening agent surplus.
2. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 1, it is characterized in that described epoxidized vegetable oil can be epoxy soybean oil, also can be epoxidised Oleum Gossypii semen, rapeseed oil, Semen Maydis oil, peanut oil, sunflower seed oil, safflower oil, or the mixture being formed by them.
3. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 1, is characterized in that described epoxy aliphatic acid methyl ester refers to take fatty acid methyl ester as raw material, the product obtaining after the art breading identical with the epoxidation of soybean oil.
4. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 3, it is characterized in that described fatty acid methyl ester can be soya fatty acid methyl esters, also can be Witconol 2301, methyl linoleate, Linolenic acid methylester, cotton oil fatty acid methyl ester, corn oil fatty acid methyl esters, rapeseed oil fatty acid methyl esters, peanut oil fatty acid methyl esters, sunflower seed oil fatty acid methyl ester, safflower oil fatty acid methyl ester, or the mixture being formed by them.
5. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 1, is characterized in that described epoxyfatty acid polyol ester refers to take polyhydric alcohol fatty acid ester as raw material, the product obtaining after the art breading identical with the epoxidation of soybean oil.
6. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 5, is characterized in that described polyol esters of fatty acids refers to take polyvalent alcohol and lipid acid as raw material, the product obtaining after esterification.
7. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 6, it is characterized in that described polyvalent alcohol can be ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, also can be propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, tetramethylolmethane, dipentaerythritol, tripentaerythritol, TriMethylolPropane(TMP), ditrimethylolpropane, three TriMethylolPropane(TMP)s, glucose, maltose, sucrose, lactose, sorbyl alcohol, N.F,USP MANNITOL, maltose alcohol, or the mixture being formed by them.
8. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 6, it is characterized in that described lipid acid can be soya fatty acid, also can be oleic acid, linolic acid, linolenic acid, cotton oil lipid acid, corn oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid, sunflower seed oil lipid acid, safflower oil lipid acid, or the mixture being formed by them.
9. the bio-based environment-friendly plasticizer that can substitute DOP completely as claimed in claim 1, it is characterized in that described cold resisting type softening agent can be triethyl citrate, also can be acetyl triethyl citrate, butyryl triethyl citrate, oleoyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, butyryl tributyl citrate, oleoyl tributyl citrate, trioctyl lemon acid, ATOC, butyryl trioctyl lemon acid, oleoyl trioctyl lemon acid, Octyl adipate, dioctyl terephthalate, citric acid tri-n-hexyl ester, ATHC, butyryl citric acid tri-n-hexyl ester, oleoyl citric acid tri-n-hexyl ester, or the mixture being formed by them.
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| WO2019039879A3 (en) * | 2017-08-25 | 2019-04-25 | 애경유화 주식회사 | Composite plasticizer composition, preparation method therefor, and polymer resin composition using same |
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