CN101993548A - Environment-friendly composite plasticizer and preparation method - Google Patents
Environment-friendly composite plasticizer and preparation method Download PDFInfo
- Publication number
- CN101993548A CN101993548A CN 201010298462 CN201010298462A CN101993548A CN 101993548 A CN101993548 A CN 101993548A CN 201010298462 CN201010298462 CN 201010298462 CN 201010298462 A CN201010298462 A CN 201010298462A CN 101993548 A CN101993548 A CN 101993548A
- Authority
- CN
- China
- Prior art keywords
- softening agent
- chemical formula
- ester
- environment
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *OC(Cc1ccc(C(O*)=I)c(C(O*)=O)c1)=O Chemical compound *OC(Cc1ccc(C(O*)=I)c(C(O*)=O)c1)=O 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
The invention discloses a plasticizer and a preparation method, in particular an environment-friendly composite plasticizer which is based on a diethylene glycol dibenzoate type plasticizer and di(2-ethylhexyl) terephthalate and can comprise epoxy compounds, adipate compounds, dicaprate compounds and trimellitate compounds. The environment-friendly composite plasticizer can be used as a main plasticizer of polyvinyl chloride resin and other resins. The invention also relates to a preparation method of the environment-friendly composite plasticizer and ingredients thereof, namely the diethylene glycol dibenzoate type plasticizer and the di(2-ethylhexyl) terephthalate. The environment-friendly composite plasticizer has the characteristics of high intermiscibility, plasticizing efficiency, cold resistance, heat resistance, pollution resistance, extraction resistance, migration, electric insulation, light and heat stability and the like, and is widely applied in plasticizing industry.
Description
Technical field
The present invention relates to a kind of chemical plasticizing agent and preparation method, specifically can be used as the environment-friendly composite softening agent of polyvinyl chloride resin primary plasticizers such as (PVC).
Technical background
Softening agent is the maximum auxiliary agent kind of modern plastics industry, accounts for 60% of additives for plastics ultimate production, wherein, has occupied the market share more than 50% of softening agent as the phthalate of plastic plasticizer.As the dioctyl phthalate (DOP) (DOP) of primary plasticizer by american cancer institute (NCI) suspect carcinogenesis is arranged after, its use range is restricted.People are seeking and research, performance better surrogate more safer than DOP.Diethylene glycol dibenzoate (DEDB) and terephthalic acid two (2-ethyl oneself) ester (DOTP) is in the environment-friendly type softening agent modal two kinds, can replace DOP to use as primary plasticizer, has application value.Wherein, DEDB plasticizer molecule amount and molecular polarity are all bigger, and be good with the polyvinyl chloride resin intermiscibility, has the plasticizing efficiency height, and anti-pollution and resistance to persistence are good, but its fusing point is low, and be solid winter, uses inconvenience.And DOTP is the isomers of DOP, because structural difference than DOP better electric durability, thermotolerance, anti-extractable, resistance to migration are arranged, but plasticizing capacity is lower than DOP.Other softening agent such as epoxies, aliphatics polybasic ester class, trimellitate class etc. all have own particular performances, but because of relatively poor with the resin intermiscibility, fail to be used widely.Therefore, two or more environment-friendly plasticizer is mixed composite,, just becoming a kind of trend to obtain the compound softening agent of good comprehensive properties.
Be subjected to the restriction of state's environmental regulations such as European Union, the U.S., the softening agent product transforms to the direction of low toxicity, environmental protection gradually.Develop the most important thing nontoxic, that environment-friendly polyvinyl chloride elasticizer becomes softening agent enterprise raising core competitiveness.
Softening agent is a kind of plastics additive, be resin such as PVC when carrying out forming process for improve its processing characteristics or by improve the performance of resin own deficiency some compounds that must add.The ideal softening agent should have following performance: (1) has good intermiscibility with resin; (2) plasticizing efficiency height; (3) stable to hot light; (4) volatility is low; (5) transport property is little; (6) extraction of water-fast, oil and organic solvent; (7) electrical insulating property is good; (8) asepsis environment-protecting; (9) fungus resistance is good; (10) stain resistance is good; (11) inexpensive.At present, common environment-friendly type softening agent mainly contains phenylformic acid polyol ester class, epoxy compounds, aliphatics polybasic ester class, trimellitate class etc.
The composite mixing of multiple softening agent back is obtained a kind of new softening agent product, to give the resin good comprehensive performances, reach satisfied plasticization effect, this way has obtained the approval of more and more producers.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly composite softening agent, make resins such as itself and PVC have good intermiscibility, the plasticizing efficiency height, cold-resistant, heat-resisting, anti-pollution, anti-extraction, transport property is good, and electrical insulating property is good, and is stable to photo-thermal.
For achieving the above object, the invention provides a kind of environment-friendly composite softening agent, comprise following at least two kinds of compositions:
A kind of environment-friendly composite softening agent is characterized in that: comprise following two kinds of compositions at least:
A) DEDB class softening agent is specially the mixture of diethylene glycol dibenzoate or dipropylene glycol dibenzoate or above two kinds of materials; With
B) terephthalic acid two (the 2-ethyl is own) ester.
As preferably, the mass content of the composition in the above-mentioned environment-friendly composite softening agent is as follows,
A) mixture of the diethylene glycol dibenzoate of the dipropylene glycol dibenzoate of the diethylene glycol dibenzoate of 20～70wt% or 20～70wt% or 20～70wt% and dipropylene glycol dibenzoate; With
B) terephthalic acid two of 20～80wt% (the 2-ethyl is own) ester.
As preferably, the softening agent described in the above-mentioned environment-friendly composite softening agent comprises one or more in the following substances, the epoxy compounds of Chemical formula 1-1 expression; And the adipic acid ester compounds of Chemical formula 1-2 expression; And the sebate compounds of Chemical formula 1-3 expression; And the trimellitic acid ester compound of Chemical formula 1-4 expression,
The mass percent that each component accounts for softening agent is:
A) epoxy compounds of Chemical formula 1-1 expression is 0.01～40wt%;
B) the adipic acid ester compounds of Chemical formula 1-2 expression is 0.01～20wt%;
C) the sebate compounds of Chemical formula 1-3 expression is 0.0.01～20wt%;
D) the trimellitic acid ester compound of Chemical formula 1-4 expression is 0.01～20wt%;
Chemical formula is respectively:
R wherein
1And R
2Respectively do for oneself and have the alkyl of 2 to 13 carbon atoms;
R wherein
3And R
4Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms;
R wherein
5And R
6Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms;
R wherein
7, R
8And R
9Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms.
As preferably, the material in the above-mentioned environment-friendly composite softening agent is as follows:
A) compound of Chemical formula 1-1 is an epoxy aliphatic acid methyl ester;
B) compound of Chemical formula 1-2 is hexanodioic acid two (the 2-ethyl is an own) ester;
C) compound of Chemical formula 1-3 is sebacic acid two (the 2-ethyl is an own) ester;
D) compound of Chemical formula 1-4 is tri trimellitate (the 2-ethyl is an own) ester;
And comprise above-mentioned four kinds of compounds in the softening agent simultaneously.
A kind of preparation method of environment-friendly composite softening agent is characterized in that comprising the steps:
A) under 200～280 ℃ with following substance reaction 10～26 hours:
I) glycol ether of the phenylformic acid of 68wt%～75wt% and 25wt%～32wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer; Or
Ii) the dipropylene glycol of the phenylformic acid of 63wt%～70wt% and 30%～37wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer; Or
Iii) the dipropylene glycol of the glycol ether of the phenylformic acid of 63%～75wt% and 1wt%～32wt% and 1%～37wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer;
B) holding temperature vacuumizes the unreacted acid of sloughing in the step a) at 220～280 ℃;
C) adopt the hydrogen peroxide of 0.2～2wt% that the reactant in the step b) is decoloured;
D) reactant in the step c) is dewatered, again super-cell is put in the reactant after the dehydration, and with its press filtration;
E) preparation of terephthalic acid two (the 2-ethyl is own) ester:
The terephthalic acid of 35wt%～40wt% and the 2-Ethylhexyl Alcohol of 60wt%～65wt% mix and account for the tetrabutyl titanate of preceding two kinds of substance weight 0.01～1wt%; Reacted 4～16 hours down at 180～260 ℃;
F) adopt in the sodium carbonate solution of 0.5～5wt% and e) reactant in tetrabutyl titanate, yellow soda ash equates with the molar equivalent of tetrabutyl titanate;
G) under 100～200 ℃ with f) reactant stripping 30～90 minutes, slough unreacting alcohol; With
H) super-cell is put into g) reactant in, with its press filtration;
I) with step d) and step h) reactant of preparation places mixing tank evenly to mix, and obtains the environment-friendly composite softening agent.
Embodiment
Below enforcement of the present invention is specified:
Embodiment 1
The terephthalic acid two of the diethylene glycol dibenzoate 70wt% of 30wt% (the 2-ethyl is own) ester mixes the softening agent of forming.
Embodiment 2
The dipropylene glycol dibenzoate of 50wt% and the terephthalic acid of 50wt% two (the 2-ethyl is own) ester mixes the softening agent of forming.
Embodiment 3
The mixture of the diethylene glycol dibenzoate of 35wt% and 30% dipropylene glycol dibenzoate and the terephthalic acid of 35wt% two (the 2-ethyl is own) ester mixes the softening agent of forming.
Embodiment 4
The terephthalic acid two of the diethylene glycol dibenzoate 60wt% of 30wt% (the 2-ethyl is own) ester, and 10% epoxy aliphatic acid methyl ester mix the softening agent of forming.
Embodiment 5
The dipropylene glycol dibenzoate of 50wt% and the terephthalic acid of 35wt% two (the 2-ethyl is own) ester, and 15% hexanodioic acid two (the 2-ethyl is own) ester mix the softening agent of forming.
Embodiment 6
The mixture of the diethylene glycol dibenzoate of 25wt% and 34% dipropylene glycol dibenzoate and the terephthalic acid of 35wt% two (the 2-ethyl is own) ester, and 6% tri trimellitate (the 2-ethyl is own) ester mixes the softening agent of forming.
Embodiment 7
The mixture of the diethylene glycol dibenzoate of 25wt% and 30% dipropylene glycol dibenzoate, with the terephthalic acid two of 35wt% (2-ethyl oneself) ester, and respectively get 2.5% epoxy aliphatic acid methyl ester, hexanodioic acid two (2-ethyl oneself) ester, sebacic acid two (2-ethyl oneself) ester, tri trimellitate (2-ethyl oneself) ester and mix the softening agent of forming.
In the foregoing description, a kind of composition of environment-friendly composite softening agent of the present invention is a DEDB class softening agent, DEDB class softening agent of the present invention is diethylene glycol dibenzoate (DEDB) and dipropylene glycol dibenzoate (DPGDB), characteristics such as wherein DEDB has that intermiscibility is good, winter hardiness is good, static resistance, antifouling property are remarkable, and toxicity is low, LD
50Be 5.44g/kg.Administrative authoritys such as external related food, makeup, medicine think that DEDB is a kind of bigger softening agent of security that can be used for the contact food wrapping material, but its shortcoming is that fusing point is higher, is solid during cold snap, has limited its application; Another kind of dipropylene glycol dibenzoate (DPGDB), though fusing point is low, superior performance, on the high side.
The another kind of composition of environment-friendly composite softening agent of the present invention is terephthalic acid two (the 2-ethyl is an own) ester (DOTP), DOTP is the primary plasticizer of a kind of excellent property of using of PVC plastics, it is compared with DOP has advantages such as heat-resisting, cold-resistant, difficult volatilization, anti-extraction, flexibility and electrical insulation capability are good, in goods, demonstrate good persistence, anti-soap water-based and low-temperature pliability, but plasticizing capacity is poor.
Therefore, in the present invention that DEDB class softening agent and terephthalic acid two (the 2-ethyl is own) ester mixing is composite, obtain the superior environment-friendly composite softening agent of over-all properties.
Yet, only use DEDB class softening agent and terephthalic acid two (the 2-ethyl is own) two kinds of compositions of ester can not satisfy the property of some softening agent.Require to have stronger ageing resistance, winter hardiness, thermotolerance as some softening agent.
Embodiment 8
The preparation of softening agent:
A) under 250 ℃ with following substance reaction 20 hours:
The phenylformic acid of 70wt% and the glycol ether of 30wt% are that raw material and the heteropolyacid that accounts for raw material 1wt% are catalyzer;
B) holding temperature vacuumizes the unreacted acid of sloughing in the step a) at 260～280 ℃;
C) adopt the hydrogen peroxide of 1.2wt% that the reactant in the step b) is decoloured;
D) reactant in the step c) is dewatered, again super-cell is put in the reactant after the dehydration, and with its press filtration;
E) preparation of terephthalic acid two (the 2-ethyl is own) ester:
The terephthalic acid of 40wt% and the 2-Ethylhexyl Alcohol of 60wt% mix and account for the tetrabutyl titanate of preceding two kinds of substance weight 1wt%; Reacted 10 hours down at 180～200 ℃;
F) adopt in the sodium carbonate solution of 3.5wt% and e) reactant in tetrabutyl titanate, yellow soda ash equates with the molar equivalent of tetrabutyl titanate;
G) under 130 ℃ with f) reactant stripping 60 minutes, slough unreacting alcohol; With
H) super-cell is put into g) reactant in, with its press filtration;
I) with step d) and step h) reactant of preparation places mixing tank evenly to mix, and obtains the environment-friendly composite softening agent.
Claims (5)
1. environment-friendly composite softening agent is characterized in that: comprise following compositions at least:
A) DEDB class softening agent is specially: the mixture of diethylene glycol dibenzoate or dipropylene glycol dibenzoate or above two kinds of materials; With
B) terephthalic acid two (the 2-ethyl is own) ester.
2. according to the environment-friendly composite softening agent of right 1 requirement, it is characterized in that: the mass content of component is as follows,
A) mixture of the diethylene glycol dibenzoate of the dipropylene glycol dibenzoate of the diethylene glycol dibenzoate of 20～70wt% or 20～70wt% or 20～70wt% and dipropylene glycol dibenzoate; With
B) terephthalic acid two of 20～80wt% (the 2-ethyl is own) ester.
3. according to the environment-friendly composite softening agent of right 1 requirement, it is characterized in that: softening agent comprises one or more in the following substances, the epoxy compounds of Chemical formula 1-1 expression; And the adipic acid ester compounds of Chemical formula 1-2 expression; And the sebate compounds of Chemical formula 1-3 expression; And the trimellitic acid ester compound of Chemical formula 1-4 expression,
The mass percent that each component accounts for softening agent is:
A) epoxy compounds of Chemical formula 1-1 expression is 0.01～40wt%;
B) the adipic acid ester compounds of Chemical formula 1-2 expression is 0.01～20wt%;
C) the sebate compounds of Chemical formula 1-3 expression is 0.01～20wt%;
D) the trimellitic acid ester compound of Chemical formula 1-4 expression is 0.01～20wt%;
Chemical formula is respectively:
R wherein
1And R
2Respectively do for oneself and have the alkyl of 2 to 13 carbon atoms;
R wherein
3And R
4Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms;
R wherein
5And R
6Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms;
R wherein
7, R
8And R
9Respectively do for oneself and have the alkyl of 4 to 13 carbon atoms.
4. environment-friendly composite softening agent according to claim 3 is characterized in that, and is described
A) compound of Chemical formula 1-1 is an epoxy aliphatic acid methyl ester;
B) compound of Chemical formula 1-2 is hexanodioic acid two (the 2-ethyl is an own) ester;
C) compound of Chemical formula 1-3 is sebacic acid two (the 2-ethyl is an own) ester;
D) compound of Chemical formula 1-4 is tri trimellitate (the 2-ethyl is an own) ester;
And comprise above-mentioned four kinds of compounds in the softening agent simultaneously.
5. the preparation method of an environment-friendly composite softening agent is characterized in that comprising the steps:
A) under 200～280 ℃ with following substance reaction 10～26 hours:
I) glycol ether of the phenylformic acid of 68wt%～75wt% and 25wt%～32wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer; Or
Ii) the dipropylene glycol of the phenylformic acid of 63wt%～70wt% and 30%～37wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer; Or
Iii) the dipropylene glycol of the glycol ether of the phenylformic acid of 63%～75wt% and 1wt%～32wt% and 1%～37wt% is that raw material and the heteropolyacid that accounts for raw material 0.01～1wt% are catalyzer;
B) holding temperature vacuumizes the unreacted acid of sloughing in the step a) at 220～280 ℃;
C) adopt the hydrogen peroxide of 0.2～2wt% that the reactant in the step b) is decoloured;
D) reactant in the step c) is dewatered, again super-cell is put in the reactant after the dehydration, and with its press filtration;
E) preparation of terephthalic acid two (the 2-ethyl is own) ester:
The terephthalic acid of 35wt%～40wt% and the 2-Ethylhexyl Alcohol of 60wt%～65wt% mix and account for the tetrabutyl titanate of preceding two kinds of substance weight 0.01～1wt%; Reacted 4～16 hours down at 180～260 ℃;
F) tetrabutyl titanate in the reactant sodium carbonate solution neutralization procedure e of employing 0.5～5wt%), yellow soda ash equates with the molar equivalent of tetrabutyl titanate;
G) under 100～200 ℃ with the reactant stripping of step f) 30～90 minutes, slough unreacting alcohol;
H) super-cell is put in the reactant of step g), its press filtration;
I) with step d) and step h) reactant of preparation places mixing tank evenly to mix, and obtains the environment-friendly composite softening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010298462 CN101993548A (en) | 2010-09-30 | 2010-09-30 | Environment-friendly composite plasticizer and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010298462 CN101993548A (en) | 2010-09-30 | 2010-09-30 | Environment-friendly composite plasticizer and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101993548A true CN101993548A (en) | 2011-03-30 |
Family
ID=43784342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010298462 Pending CN101993548A (en) | 2010-09-30 | 2010-09-30 | Environment-friendly composite plasticizer and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101993548A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650332A (en) * | 2014-12-09 | 2015-05-27 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| US9193844B2 (en) | 2012-06-29 | 2015-11-24 | Oxea Gmbh | Mixtures containing trimellitic acid ester and polyether polyol ester as plasticizers, use of the mixtures for producing polymer compounds and PVC materials containing said mixtures |
| CN105295102A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing green environment-friendly plasticizer |
| CN105295396A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing plasticizer applied to automobile rubber and plastic accessory |
| CN105348560A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Heat-resisting anti-aging plasticizer composition |
| CN105638656A (en) * | 2014-12-02 | 2016-06-08 | 龙灯农业化工国际有限公司 | Agricultrue chemical composition, preparation and application thereof |
| CN106317450A (en) * | 2016-09-27 | 2017-01-11 | 辽阳合成催化剂有限公司 | Composite modified environment-friendly plasticizing agent |
| CN106832434A (en) * | 2017-03-13 | 2017-06-13 | 四川群青新材料科技有限公司 | For plasticiser prepared by plastics |
| CN108350154A (en) * | 2016-06-20 | 2018-07-31 | 株式会社Lg化学 | Plasticizer composition, resin combination and preparation method thereof |
| CN109134926A (en) * | 2018-06-25 | 2019-01-04 | 西安医学院 | A kind of Compositional type environment-friendly plasticizer and preparation method thereof for Corvic |
| CN109294116A (en) * | 2018-09-18 | 2019-02-01 | 江苏瑞佳新材料有限公司 | A kind of preparation method of PVC plasticizer |
| CN110760139A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | High-resistivity flame-retardant polyvinyl chloride cable material composition |
| CN111040246A (en) * | 2019-11-14 | 2020-04-21 | 东莞市世泰贸易有限公司 | Improved preparation method of dioctyl adipate |
| CN111187477A (en) * | 2018-01-02 | 2020-05-22 | 金华观瑞科技有限公司 | PVC composition containing ester plasticizer |
| TWI719208B (en) * | 2016-05-18 | 2021-02-21 | 南韓商Ｌｇ化學股份有限公司 | Plasticizer composition, resin composition and methods of preparing the same |
| TWI733984B (en) * | 2017-02-10 | 2021-07-21 | 南韓商Ｌｇ化學股份有限公司 | Plasticizer composition and resin composition including the same |
| WO2023281945A1 (en) * | 2021-07-06 | 2023-01-12 | Dic株式会社 | Plasticizer composition for vinyl chloride resin, plastisol and coating thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498246A (en) * | 2001-01-19 | 2004-05-19 | ά | Polymer compositions comprising telomers and articles or parts using these compositions |
| CN101238091A (en) * | 2005-08-12 | 2008-08-06 | 伊士曼化工公司 | Production of di-(2-ethylhexyl) terephthalate |
| US20090029107A1 (en) * | 2007-07-26 | 2009-01-29 | Pyn, S.A. De C.V. | Decorative and protective nonslip covering of multiple uses and the production process and composition thereof |
-
2010
- 2010-09-30 CN CN 201010298462 patent/CN101993548A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498246A (en) * | 2001-01-19 | 2004-05-19 | ά | Polymer compositions comprising telomers and articles or parts using these compositions |
| CN101238091A (en) * | 2005-08-12 | 2008-08-06 | 伊士曼化工公司 | Production of di-(2-ethylhexyl) terephthalate |
| US20090029107A1 (en) * | 2007-07-26 | 2009-01-29 | Pyn, S.A. De C.V. | Decorative and protective nonslip covering of multiple uses and the production process and composition thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《辽宁化工》 19920430 吴庆银 杂多酸催化合成DEDB增塑剂的研究 第38-40页 5 , 第2期 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9193844B2 (en) | 2012-06-29 | 2015-11-24 | Oxea Gmbh | Mixtures containing trimellitic acid ester and polyether polyol ester as plasticizers, use of the mixtures for producing polymer compounds and PVC materials containing said mixtures |
| US9580573B2 (en) | 2012-06-29 | 2017-02-28 | Oxea Gmbh | Mixtures containing trimellitic acid ester and polyether polyol ester as plasticizers, use of the mixtures for producing polymer compounds and PVC materials containing said mixtures |
| CN105638656A (en) * | 2014-12-02 | 2016-06-08 | 龙灯农业化工国际有限公司 | Agricultrue chemical composition, preparation and application thereof |
| CN104650332A (en) * | 2014-12-09 | 2015-05-27 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| CN105295396A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing plasticizer applied to automobile rubber and plastic accessory |
| CN105295102A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing green environment-friendly plasticizer |
| CN105348560A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Heat-resisting anti-aging plasticizer composition |
| US11572453B2 (en) * | 2016-05-18 | 2023-02-07 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
| US11427699B2 (en) | 2016-05-18 | 2022-08-30 | Lg Chem, Ltd. | Plasticizer composition, resin composition and methods of preparing the same |
| TWI719208B (en) * | 2016-05-18 | 2021-02-21 | 南韓商Ｌｇ化學股份有限公司 | Plasticizer composition, resin composition and methods of preparing the same |
| US10865289B2 (en) | 2016-06-20 | 2020-12-15 | Lg Chem, Ltd. | Plasticizer composition, resin composition and methods of preparing the same |
| CN108350154A (en) * | 2016-06-20 | 2018-07-31 | 株式会社Lg化学 | Plasticizer composition, resin combination and preparation method thereof |
| CN108350154B (en) * | 2016-06-20 | 2020-12-25 | 株式会社Lg化学 | Plasticizer composition, resin composition and method for producing the same |
| CN106317450A (en) * | 2016-09-27 | 2017-01-11 | 辽阳合成催化剂有限公司 | Composite modified environment-friendly plasticizing agent |
| TWI733984B (en) * | 2017-02-10 | 2021-07-21 | 南韓商Ｌｇ化學股份有限公司 | Plasticizer composition and resin composition including the same |
| US11499030B2 (en) | 2017-02-10 | 2022-11-15 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
| CN106832434A (en) * | 2017-03-13 | 2017-06-13 | 四川群青新材料科技有限公司 | For plasticiser prepared by plastics |
| CN111187477A (en) * | 2018-01-02 | 2020-05-22 | 金华观瑞科技有限公司 | PVC composition containing ester plasticizer |
| CN109134926A (en) * | 2018-06-25 | 2019-01-04 | 西安医学院 | A kind of Compositional type environment-friendly plasticizer and preparation method thereof for Corvic |
| CN110760139A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | High-resistivity flame-retardant polyvinyl chloride cable material composition |
| CN110760139B (en) * | 2018-07-27 | 2021-10-22 | 中国石油化工股份有限公司 | High-resistivity flame-retardant polyvinyl chloride cable material composition |
| CN109294116B (en) * | 2018-09-18 | 2020-07-31 | 江苏瑞佳新材料有限公司 | Preparation method of PVC plasticizer |
| CN109294116A (en) * | 2018-09-18 | 2019-02-01 | 江苏瑞佳新材料有限公司 | A kind of preparation method of PVC plasticizer |
| CN111040246A (en) * | 2019-11-14 | 2020-04-21 | 东莞市世泰贸易有限公司 | Improved preparation method of dioctyl adipate |
| WO2023281945A1 (en) * | 2021-07-06 | 2023-01-12 | Dic株式会社 | Plasticizer composition for vinyl chloride resin, plastisol and coating thereof |
| JP7384324B2 (en) | 2021-07-06 | 2023-11-21 | Dic株式会社 | Plasticizer composition for vinyl chloride resin, plastisol and its coating film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101993548A (en) | Environment-friendly composite plasticizer and preparation method | |
| CN101857707B (en) | Environmental-protection type PVC/ABS plastic alloy material and preparation method thereof | |
| CN103146156B (en) | Flame-retardant polyester resin composition | |
| CN102020825A (en) | Flame-retardant permanent antistatic ABS material and preparation method thereof | |
| CN105622909B (en) | A kind of preparation method and applications of aqueous alkide resin | |
| CN101709133A (en) | Excellent anti-aging ABS composite material and preparation method thereof | |
| CN102924884A (en) | PBT (polybutylece terephthalate) composite and preparation method thereof | |
| CN103059471A (en) | Environment-friendly nontoxic high-insulation low temperature-resistant polyvinyl chloride cable material and preparation process thereof | |
| CN103289151B (en) | Environment-friendly type soft NBR/PVC Blend rubber and preparation method | |
| CN106589590A (en) | Flame-retardant polypropylene | |
| CN115073499B (en) | Antibacterial rare earth compound and application thereof | |
| CN108485191B (en) | Epoxy resin composition with excellent flame retardance and flame retardance durability and preparation method thereof | |
| CN103435944A (en) | Environment-friendly calcium-zinc composite heat stabilizer | |
| CN108424513B (en) | N-B synergistic high-flame-retardant curing agent and synthetic method thereof | |
| CN106280106A (en) | Electric wire high temperature resistant environment-protective nontoxic calcium zinc stabilizer and production method thereof | |
| CN102875931B (en) | Preparation process of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride) | |
| CN106317461A (en) | Synthesis preparation method of intercalation polymerization efficient nontoxic environment-friendly calcium-zinc stabilizer | |
| CN109776780A (en) | A kind of phosphor-containing flame-proof PTT and its preparation method and application | |
| CN103664613A (en) | Nonlinear plasticizer and preparation method and application thereof | |
| CN101602672A (en) | Terephthalic acid two (2-propyl group heptan) ester and its production and application | |
| CN106280322A (en) | PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods | |
| CN104045856A (en) | Catalytic-expansion-type alcohol-soluble nylon modified flame retardant and preparation method thereof | |
| CN103146059A (en) | Polypropylene modified halogen-free flame retardant composite material and preparation method thereof | |
| CN103555222A (en) | Flame retardant white emulsion and preparation method thereof | |
| CN103467932B (en) | PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110330 |