CN102226013A - Method for producing cold-resistant plasticizer through by-product nylon acids - Google Patents
Method for producing cold-resistant plasticizer through by-product nylon acids Download PDFInfo
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- CN102226013A CN102226013A CN2011101148375A CN201110114837A CN102226013A CN 102226013 A CN102226013 A CN 102226013A CN 2011101148375 A CN2011101148375 A CN 2011101148375A CN 201110114837 A CN201110114837 A CN 201110114837A CN 102226013 A CN102226013 A CN 102226013A
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Abstract
The invention discloses a method for producing a cold-resistant plasticizer through by-product nylon acids, and belongs to the technical field of nylon acid integrated utilization and plasticizer technology. In the invention, industrial by-product nylon acids replace high-valent dibasic acids and are synthesized into special cold-resistant plastic additive nylon acid dibutyl ester products thus an integrated utilization of by-product is realized and a production cost is reduced. The nylon acid dibutyl ester products produced the method have the characteristics of a color number (Pt-Co) less than or equal to 100, an acid value less than or equal to 0.3 mp KOH/g and a density in a range of 0.94 to 0.96 g/cm <3>, good low temperature characteristics and favorable compatibility of polyvinyl chloride (PVC) high-molecular materials, and reach requirements of product processing.
Description
Technical field
A kind of method of utilizing by product nylon acid production cold resistant plasticizer belongs to nylon acid comprehensive utilization and plastic plasticizer technical field.
Background technology
The lipid acid dibasic ester has a wide range of applications in organic polymer material processing and in using as a kind of cold resisting type softening agent of special type, the cold resisting type softening agent of suitability for industrialized production mainly is with adipic acid at present, the isometric carbochain diprotic acid of sebacic acid carries out esterification as raw material and 2-ethylhexanol and is prepared, because factors such as cost of material, this type of product application is restricted, the present invention utilizes suitability for industrialized production by product nylon acid, the synthetic extraordinary cold resistant plasticizer of comprehensive utilization, make the byproduct comprehensive utilization, the long carbochain biatomic acid that substitute valence is high, reduce raw materials cost, product can all high with part substitute valence adipic acid dioctyl ester, the dioctyl sebacate softening agent, also alternative phthalic acid two (2-ethyl) ester is applied in the low temperature PVC goods, the consistency of made softening agent and PVC is good, winter hardiness is good, and more wide application prospect is arranged.
Summary of the invention
The object of the invention provides a kind of method of utilizing by product nylon acid production cold resistant plasticizer, utilize industrial production by product nylon acid to be raw material, the long carbochain biatomic acid that substitute valence is high, the synthetic extraordinary winter hardiness additives for plastics of comprehensive utilization, make the byproduct comprehensive utilization, reduce production costs.
The major ingredient of by product nylon acid is the mixture of Succinic Acid, pentanedioic acid and hexanodioic acid.Reaction principle is that nylon acid and propyl carbinol carry out esterification under the vitriolic katalysis, and reaction formula is as follows:
The first step fast response generates the nylon acid mono; Second step need be in the presence of catalyzer, in higher temperature and long reaction times, and this second step be reversible reaction, finally generate dibutylester nylon acids.For make balance to esterification completely direction move, in reaction system, adopt excessive propyl carbinol, utilize propyl carbinol and water can form the effect of hydrogen bond, along with the carrying out of the raising and the reaction of temperature, constantly remove the water of generation, can form its composition of binary azeotrope according to propyl carbinol and water: propyl carbinol 62%, water 38%, this character that the binary azeotrope boiling point is 92.4 ℃, constant boiling mixture is steamed, allow its condensation layering again, the propyl carbinol on upper strata turns back in the reactor, and lower layer of water is emitted.The continuous like this balance of breaking reaction farthest makes the reaction raw materials nylon acid change into ester, can obtain the productive rate of higher target product.
Production technique is through over-churning, neutralization, washing, dealcoholysis and filter operation.Its synthetic route schema as shown in Figure 1.
Technical scheme of the present invention: a kind of method of utilizing by product nylon acid production cold resistant plasticizer, utilize industrial production by product nylon acid to be raw material, its main composition is the mixture of Succinic Acid, pentanedioic acid and hexanodioic acid, solid nylon acid and propyl carbinol carry out esterification, with the protonic acid vitriol oil is catalyzer, dewater in the reaction process and need not be with aqua, but utilize alcohol excess to remove generation water with the effect formation binary azeotropic principle of hydrogen bond, Ni Long Suan ︰ propyl carbinol mass ratio is 1 ︰ 1.9 ~ 2.1,120 ~ 130 ℃ of esterification temperatures, reaction times 4h; Through neutralization, washing, dealcoholysis and filtration, get the dibutylester nylon acids product then.
140 ℃ ~ 145 ℃ of dealcoholysis temperature, vacuum tightness is 70 ~ 80kpa.
The principal character of product: color and luster (Pt-Co)≤100, saponification value 450 ~ 460 mg KOH/g, acid number≤0.3 mg KOH/g, density 0.94 ~ 0.96 g/cm
3, weight loss on heating≤3.0%.
Beneficial effect of the present invention: the present invention utilizes the synthetic extraordinary cold resistant plasticizer of suitability for industrialized production by product nylon acid comprehensive utilization, make the byproduct comprehensive utilization, the long carbochain biatomic acid that substitute valence is high, reduce raw materials cost, product can high adipic acid dioctyl ester, the dioctyl sebacate softening agent of all or part of substitute valence, also alternative phthalic acid two (2-ethyl) ester is applied in the low temperature PVC goods, the consistency of made softening agent and PVC is good, winter hardiness is good, and more wide application prospect is arranged.
Description of drawings
The process flow diagram of Fig. 1 by product nylon acid production cold resistant plasticizer.
Embodiment
Embodiment 1
Nylon acid 3.0kg, propyl carbinol 5.9kg (Ni Long Suan ︰ propyl carbinol=1 ︰, 1.97 mass ratioes) drops into esterifying kettle, adds catalyst sulfuric acid 0.023kg, and gac 0.05kg stirs and heats up 120 ~ 130 ℃ of esterification temperatures, reaction times 4h.When treating that aquifer yield reaches theoretical value, react completely the back esterifying liquid under 60 ℃ ~ 65 ℃ temperature, sodium carbonate solution neutralization with 5%, standing demix, the ester layer washs with warm water, and the thick ester after the washing is sloughed excessive propyl carbinol under vacuum, 140 ℃ ~ 145 ℃ of temperature, vacuum tightness is 70 ~ 80kpa, treats that thick ester flash-point greater than 130 ℃ (open cup), stops dealcoholysis.Thick ester after the dealcoholysis promptly gets the dibutylester nylon acids finished product after filtration, finished product leading indicator such as following table 1.
Table 1 esterification products data
* Ni Long Suan ︰ propyl carbinol=1 ︰, 2.1 mass ratioes
Application Example 1
Product is hanged down the mensuration of gentle Qu Wendu: low gentle Qu Wendu (T
f℃) press ASTMD1043-61T, to measure with the Clash-Berg method, it is T as a result
f℃ be-53 ℃, compare low 14 ℃ (DOP is-39 ℃) with phthalic acid two (2-ethyl) ester (DOP), illustrate to have lower low-temperature performance.
Consistency in PVC is measured: observe with the circle test method(s) and (press ASTM, D329), the result did not all have the phenomenon of oozing out in 1 day and 7 days, illustrate that this softening agent and PVC have consistency preferably, product application in the PVC membrane product, and is compared data with main cold resistant plasticizer Octyl adipate (DOA) and lists in table 2.Illustrate that both plasticization effects are close.
PVC membrane product plastics performance after table 2 application nylon acid di-n-butyl or the DOA plasticising
Claims (3)
1. method of utilizing by product nylon acid production cold resistant plasticizer, it is characterized in that utilizing industrial production by product nylon acid to be raw material, its main composition is the mixture of Succinic Acid, pentanedioic acid and hexanodioic acid, solid nylon acid and propyl carbinol carry out esterification, with the protonic acid vitriol oil is catalyzer, dewater in the reaction process and need not be with aqua, but utilize alcohol excess to remove generation water with the effect formation binary azeotropic principle of hydrogen bond, Ni Long Suan ︰ propyl carbinol mass ratio is 1 ︰ 1.9 ~ 2.1,120 ~ 130 ℃ of esterification temperatures, reaction times 4h; Through neutralization, washing, dealcoholysis and filtration, get the dibutylester nylon acids product then.
2. the method for utilizing by product nylon acid production cold resistant plasticizer according to claim 1 is characterized in that 140 ℃ ~ 145 ℃ of dealcoholysis temperature, and vacuum tightness is 70 ~ 80kpa.
3. the method for utilizing by product nylon acid production cold resistant plasticizer according to claim 1, the principal character that it is characterized in that product: color and luster (Pt-Co)≤100, saponification value 450 ~ 460 mg KOH/g, acid number≤0.3 mg KOH/g, density 0.94 ~ 0.96 g/cm
3, weight loss on heating≤3.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101148375A CN102226013A (en) | 2011-05-05 | 2011-05-05 | Method for producing cold-resistant plasticizer through by-product nylon acids |
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| CN2011101148375A CN102226013A (en) | 2011-05-05 | 2011-05-05 | Method for producing cold-resistant plasticizer through by-product nylon acids |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709074A (en) * | 2013-12-30 | 2014-04-09 | 济南大学 | Preparation method and application of aliphatic C4-6 diisocyanate |
| CN104119226A (en) * | 2014-06-25 | 2014-10-29 | 桐乡市化工有限公司 | Synthetic method of novel adipate cold-resistant plasticizing agent |
| CN104130445A (en) * | 2014-07-09 | 2014-11-05 | 万华化学集团股份有限公司 | Nylon acyl dicitrate plasticizer, and preparation method and application thereof |
| CN104151744A (en) * | 2014-08-12 | 2014-11-19 | 重庆自勇科技有限公司 | Cold-resistant piercing connector |
| CN107434765A (en) * | 2016-05-25 | 2017-12-05 | 卢亭枫 | A kind of method of industrialized production di-butyl nylonic acid ester |
| CN108191649A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of dibutylester nylon acids |
| CN112457604A (en) * | 2020-11-21 | 2021-03-09 | 江西慧智科技有限公司 | Cold-resistant and high-temperature-resistant cable material and preparation method thereof |
-
2011
- 2011-05-05 CN CN2011101148375A patent/CN102226013A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《塑料助剂》 20060620 方猷泉等 耐寒增塑剂尼龙酸二正丁酯的合成新工艺 p30-32 1-3 , 第3期 * |
| 《塑料工业》 19950128 周立本等 增塑剂-尼龙酸二正丁酯的研究 p36-38 1-3 , 第1期 * |
| 《河北化工》 19970620 刘玉秀等 尼龙酸生产增塑剂的研究 p13-14 1-3 , 第2期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709074A (en) * | 2013-12-30 | 2014-04-09 | 济南大学 | Preparation method and application of aliphatic C4-6 diisocyanate |
| CN103709074B (en) * | 2013-12-30 | 2015-05-06 | 济南大学 | Preparation method and application of aliphatic C4-6 diisocyanate |
| CN104119226A (en) * | 2014-06-25 | 2014-10-29 | 桐乡市化工有限公司 | Synthetic method of novel adipate cold-resistant plasticizing agent |
| CN104130445A (en) * | 2014-07-09 | 2014-11-05 | 万华化学集团股份有限公司 | Nylon acyl dicitrate plasticizer, and preparation method and application thereof |
| CN104130445B (en) * | 2014-07-09 | 2016-08-31 | 万华化学集团股份有限公司 | Double citrate plasticizer of a kind of nylon acyl and its production and use |
| CN104151744A (en) * | 2014-08-12 | 2014-11-19 | 重庆自勇科技有限公司 | Cold-resistant piercing connector |
| CN104151744B (en) * | 2014-08-12 | 2016-08-24 | 重庆自勇科技有限公司 | Cold-resistant penetrating cable clamp |
| CN107434765A (en) * | 2016-05-25 | 2017-12-05 | 卢亭枫 | A kind of method of industrialized production di-butyl nylonic acid ester |
| CN108191649A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of dibutylester nylon acids |
| CN112457604A (en) * | 2020-11-21 | 2021-03-09 | 江西慧智科技有限公司 | Cold-resistant and high-temperature-resistant cable material and preparation method thereof |
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Application publication date: 20111026 |