CN101343380A - Method for preparing elasticizer - Google Patents
Method for preparing elasticizer Download PDFInfo
- Publication number
- CN101343380A CN101343380A CNA2008101195340A CN200810119534A CN101343380A CN 101343380 A CN101343380 A CN 101343380A CN A2008101195340 A CNA2008101195340 A CN A2008101195340A CN 200810119534 A CN200810119534 A CN 200810119534A CN 101343380 A CN101343380 A CN 101343380A
- Authority
- CN
- China
- Prior art keywords
- sodium
- reaction
- plasticizer
- softening agent
- described step
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing plasticizer. The method comprises the following steps that firstly, under the condition that the catalyzator exists, glycerol is mixed with vegetable oil, and after the reaction is finished, the intermediary product is obtained; wherein, the used catalyzator is sodium alcoholate; secondly, the acylatjng reaction is performed to the intermediary product obtained in the step one and acid anhydride, to obtain the plasticizer. In the method, a variety of commonly-used vegetable oils can all be applied, and the castor oil is optimal; the catalyzator is sodium ethoxide, sodium propoxide or sodium glycerol, wherein, the sodium glycerol is optimal. The reacting temperature of the step is 100 DEG C to 120 DEG C, the reacting time is 1 hour to 1.5 hours, and the reacting solvant is 1,4-dioxane. The method has the advantages that the preparation process of the environmental protective plasticizer is simplified, the defects that in the conventional method, the exchange of ester requires the high temperature of 250 DEG C, and the purification requires to use molecular distillation are overcome, the obtained plasticizer has an identical plasticizing effect with the DINP, which is non-poisonous and degradable, and the plasticizer has an important significance on the application of green plasticizer.
Description
Technical field
The present invention relates to a kind of method for preparing softening agent.
Background technology
Softening agent is to add in the high molecular polymer to increase material plasticity, makes it easy processing, gives the functional Chemicals of product softness, workability, also is the auxiliary agent kind of production capacity and consumption maximum up to now.
For a long time, softening agent is mainly based on adjacent benzene-type products, but along with the application of adjacent benzene class softening agent such as DOP on food, medicine industry more and more widely, the toxicity of softening agent also comes into one's own day by day.The numerous and confused response green environmental protection of enterprise notion abroad, constantly put into effect corresponding laws and regulations, when strengthening simultaneously to the home products technology barriers, domestic enterprise should be fully recognized that environmental protection not only to oneself, all be a useful engineering to society, but also be unique sharp weapon of breaking the technology trade barrier.Simultaneously, the plastic plasticizer industry has also obtained the attention of the Ministry of Science and Technology, becomes the important member of one of three big fields of tool development prospect of 21 century-field of new gradually.But among the preparation method of existing glycerolipid softening agent, side reaction easily takes place in the preparation temperature height, and the purifying technique complexity is unfavorable for industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing softening agent.
The method for preparing softening agent provided by the invention comprises the steps:
1) under the condition that catalyzer exists, glycerine is mixed with vegetables oil, obtain intermediate product after reaction finishes;
Wherein, catalyst system therefor is a sodium alkoxide;
2) intermediate product that step 1) is obtained and acid anhydrides carry out acylation reaction, obtain softening agent.
In above-mentioned preparation method's the step 1), various vegetables oil commonly used all are applicable to present method as sweet oil, Viscotrol C, Oleum Gossypii semen, preferred Viscotrol C; The catalyzer sodium alkoxide is sodium ethylate, sodium propylate or glycerol sodium, preferred glycerol sodium.The temperature of reaction of this step is 100-120 ℃, and the reaction times is 1-1.5 hour, and system solution presented homogeneous, clarification shape after reaction finished.This reaction is 1, and the 4-dioxane is to react in the reaction system of solvent.
After this step reaction finishes, reaction system is carried out underpressure distillation earlier, extract again.The distillation temperature of underpressure distillation step is 100～120 ℃, and the extraction liquid of extraction step is that volume ratio is the mixed solution of the second alcohol and water of 30-50: 70-50.
Step 2) in, acid anhydrides is diacetyl oxide, propionic anhydride or butyryl oxide, preferred diacetyl oxide; The temperature of acylation reaction is 130-150 ℃, and the reaction times is 1-1.5 hour.After the acylation reaction, the acid in the product is removed in vacuum distilling.The reaction pressure of this vacuum distilling is 0.5mbar, temperature 130-150 ℃.
Among the above-mentioned preparation method, the ratio of quality and the number of copies of glycerine, vegetables oil, catalyzer, solvent and acid anhydrides is 30-50: 20-40: 0.5-1: 100-150: 40-60.
The method for preparing softening agent provided by the invention, simplified the preparation technology of environment-friendly plasticizer, overcome that transesterify need reach 250 ℃ high temperature in the ordinary method, purifying needs to use the shortcoming of molecular distillation, the gained softening agent is identical with the plasticization effect of DINP, nontoxic, degradable, significant to the application of green softening agent.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1, preparation softening agent
20 gram Viscotrol C, 50 gram glycerine and 0.5 gram glycerol sodium in 150 gram solvents 1, are heated to 120 ℃ and reacted 1 hour in the 4-dioxane, clarify to the mixture homogeneous.Be in 85% the phosphoric acid with massfraction and glycerol sodium.Remove 1 120 ℃ of underpressure distillation, the 4-dioxane.With separating funnel standing demix deglycerizin.With volume ratio is 40: 60 ethanol/water solution extraction deglycerizin three esters, obtains intermediate product.Then 60 these intermediate products of gram and 60 gram diacetyl oxides were reacted 1 hour down at 140 ℃, vacuum distilling obtains 50 gram products (product 1) after removing acetate.
This compound is the mixture of the compound shown in following formula I and the formula II structural formula, and the quality percentage composition of compound is 60% shown in its Chinese style I structural formula.
Embodiment 2, preparation softening agent
25 gram Viscotrol C, 45 gram glycerine and 1 gram sodium propylate in 100 gram solvents 1, are heated to 100 ℃ and reacted 1.5 hours in the 4-dioxane, clarify to the mixture homogeneous.With massfraction is 85% phosphoric acid dilution post neutralization glycerol sodium.Remove 1 120 ℃ of underpressure distillation, the 4-dioxane.With separating funnel standing demix deglycerizin.With volume ratio is 40: 60 ethanol/water solution extraction deglycerizin three esters, obtains intermediate product.Then 55 these intermediate products of gram and 50 gram propionic anhydrides were reacted 1.5 hours down at 130 ℃, vacuum distilling removes propionic acid and obtains 50 gram products (product 2).
This softening agent is the mixture of the compound shown in above-mentioned formula I and the formula II structural formula, and the quality percentage composition of the compound shown in its Chinese style I structural formula is 75%.
Embodiment 3, preparation softening agent
40 gram sweet oil, 30 gram glycerine and 0.5 gram sodium ethylate in 135 gram solvents 1, are heated to 110 ℃ and reacted 1 hour in the 4-dioxane, clarify to the mixture homogeneous.Be in 85% the phosphoric acid with massfraction and glycerol sodium.Remove 1 120 ℃ of underpressure distillation, the 4-dioxane.With separating funnel standing demix deglycerizin.With volume ratio is 40: 60 ethanol/water solution extraction deglycerizin three esters, obtains intermediate product.Then 50 these intermediate products of gram and 40 gram butyryl oxides were reacted 1 hour down at 150 ℃, vacuum distilling removes butyric acid and obtains 45 gram products (product 3).
This compound is the mixture of the compound shown in following formula III and the formula IV structural formula, and wherein the quality percentage composition of the compound shown in the formula III structural formula is 80%.
The plasticization effect test of embodiment 4, softening agent
1) softening agent that the embodiment of the invention 1 and embodiment 3 are prepared, PVC etc. mix according to following proportioning, and the plasticization effect of this softening agent is measured.
PVC 100 weight parts
Ca-Zn stablizer 1.8 weight parts
Viscosity-depression agent 10 weight parts
Softening agent 80 weight parts
Wherein, used PVC is that Shenyang Chemical Co., Ltd. produces, and product type is PSH-30 (1700); Used Ca-Zn stablizer, the former Industry Co.,Ltd of moulding produces by Taiwan, and product type is CZ990; Used viscosity-depression agent is produced model D800 for Nanjing Jinling Petrochemical Co..
Get 200g PVC, and take by weighing other three kinds of materials according to said ratio, above-mentioned four kinds of materials are mixed stir 3 hours to mixing, vacuumize and removed bubble in 1 hour, keep vacuum to leave standstill 10 hours, vacuum tightness is 5*10
-3Mbar.The thickener of above-mentioned preparation is coated on the porcelain plate, and 210 degree bakings are 8 minutes in baking box, make thickness and be 0.2 millimeter PVC sheet material.
Adopt and last identical experiment proportioning and experiment condition, only will change DINP into by the softening agent that preparation method of the present invention obtains, this softening agent is to be produced by Shandong Lanfan Plastic Co., Ltd, obtains 0.2 millimeter PVC sheet material through above-mentioned steps.
Respectively above-mentioned sheet material is made long 120mm, the PVC batten of wide 10mm, according to GB1040-79 the tensile strength and the elongation at break of batten are measured, used trier is TNSTRON 3365 universal testing machines (U.S.'s Instrons), and the gained measurement result is as shown in table 1.In the table 1, compound 1 is by having added the prepared PVC batten of softening agent DINP, compound 2 is by having added the PVC batten that product 1 that embodiment 1 prepares makes as softening agent, and compound 3 is by having added the PVC batten that product 3 that embodiment 3 prepares makes as softening agent.As shown in Table 1, utilize the prepared PVC batten of softening agent provided by the invention, its performance reaches same level with the performance of the batten that adds DINP, illustrates that the softening agent and the existing softening agent that utilize this method to prepare have same plasticization effect.
The tensile strength of table 1PVC sheet material and the measurement result of elongation at break
2) softening agent that the embodiment of the invention 2 and embodiment 3 are prepared, PVC etc. mix according to following proportioning, and the plasticization effect of this softening agent is measured.
PVC 100 weight parts
Zinic stearas 2 weight parts
Calcium stearate 1 weight part
Softening agent 40 weight parts
Wherein, used PVC is that Tianjin Chemical Plant is produced, and product type is sg1; Used calcium stearate is northern Tonghua plant produced; Used Zinic stearas is produced for Beijing chemical reagents corporation.
Get 5000g PVC, and take by weighing other three kinds of materials according to said ratio, stir 1 hour to mixing with above-mentioned four kinds of materials are mixed, again in mill after 160 ℃ and 50RPM mix 1 hour, according to ISO 293-1974 said mixture is compression molded into the thick PVC sheet material of 4mm.
Adopt and last identical experiment proportioning and experiment condition, only will change DINP into by the softening agent that preparation method of the present invention obtains, this softening agent is to be produced by the blue sail plastic cement in Shandong company limited, obtains the thick PVC sheet material of 4mm through above-mentioned steps.
According to the bioassay standard of GB1040-79, respectively the tensile strength and the elongation at break of above-mentioned sheet material to be measured, used trier is INSTRON 3365 universal material test machines (U.S.'s Instron), the gained measurement result is as shown in table 2.In the table 2, compound 4 is by having added the prepared PVC batten of softening agent DINP, compound 5 is by having added the PVC batten that product 2 that the embodiment of the invention 2 prepares makes as softening agent, and compound 6 is by having added the PVC batten that product 3 that the embodiment of the invention 3 prepares makes as softening agent.As shown in Table 2, the prepared batten of patent softening agent that adopts method provided by the invention to prepare, its performance reaches same level with the performance of the batten that adds DINP, illustrates that the softening agent and the existing softening agent that utilize this method to prepare have same plasticization effect.
The tensile strength of table 2PVC sheet material and the measurement result of elongation at break
Claims (10)
1, a kind of method for preparing softening agent comprises the steps:
1) under the condition that catalyzer exists, glycerine is mixed with vegetables oil, obtain intermediate product after reaction finishes;
Wherein, described catalyzer is a sodium alkoxide;
2) intermediate product that described step 1) is obtained and acid anhydrides carry out acylation reaction, obtain described softening agent.
2, method according to claim 1 is characterized in that: in the described step 1), vegetables oil is Viscotrol C, sweet oil or Oleum Gossypii semen; Described sodium alkoxide is sodium ethylate, sodium propylate or glycerol sodium;
Described step 2) in, acid anhydrides is diacetyl oxide, propionic anhydride or butyryl oxide.
3, method according to claim 2 is characterized in that: in the described step 1), vegetables oil is a Viscotrol C, and sodium alkoxide is a glycerol sodium; Described step 2) in, acid anhydrides is a diacetyl oxide.
4, according to the arbitrary described method of claim 1-3, it is characterized in that: the ratio of quality and the number of copies of described glycerine, vegetables oil, catalyzer and acid anhydrides is 30-50: 20-40: 0.5-1: 40-60.
5, according to the arbitrary described method of claim 1-3, it is characterized in that: in the described step 1), temperature of reaction is 100-120 ℃, and the reaction times is 1-1.5 hour;
Described step 2) in, the temperature of acylation reaction is 130-150 ℃, and the reaction times is 1-1.5 hour.
6, method according to claim 5 is characterized in that: described step 2), the temperature of acylation reaction is 140 ℃, and the reaction times is 1 hour.
7, according to the arbitrary described method of claim 1-3, it is characterized in that: in the described step 1), after described reaction finished, with the underpressure distillation of reaction system elder generation, extraction obtained described intermediate product again.
8, method according to claim 7 is characterized in that: the distillation temperature of described underpressure distillation step is 100～120 ℃, and the extraction liquid of described extraction step is that volume ratio is the mixed solution of the second alcohol and water of 3-5: 5-7.
9, according to the arbitrary described method of claim 1-3, it is characterized in that: described glycerine and vegetables oil are 1, blended in the 4-dioxane.
10, method according to claim 9 is characterized in that: the mass fraction of described 1,4 dioxane is 100-150.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101195340A CN101343380B (en) | 2008-09-02 | 2008-09-02 | Method for preparing elasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101195340A CN101343380B (en) | 2008-09-02 | 2008-09-02 | Method for preparing elasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101343380A true CN101343380A (en) | 2009-01-14 |
| CN101343380B CN101343380B (en) | 2011-06-01 |
Family
ID=40245500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101195340A Active CN101343380B (en) | 2008-09-02 | 2008-09-02 | Method for preparing elasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101343380B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648237A (en) * | 2009-09-30 | 2012-08-22 | 陶氏环球技术有限责任公司 | Acetylated derivatives of castor oil and their blends with epoxidized fatty acid esters |
| CN105038261A (en) * | 2015-06-18 | 2015-11-11 | 张家港市大能塑料制品有限公司 | Environment-friendly plasticizer |
| CN109251444A (en) * | 2018-11-07 | 2019-01-22 | 长沙小如信息科技有限公司 | Plasticizer for polyvinyl chloride and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1025788C (en) * | 1989-03-11 | 1994-08-31 | 王利生 | Preparation of polyethylene plasticizers from oil and fats of animal or vegetable |
| CN100580025C (en) * | 2007-02-27 | 2010-01-13 | 张伟明 | Method for producing epoxy plasticizer from dirty oil and vegetable and animal waste oil |
| CN100590188C (en) * | 2007-05-22 | 2010-02-17 | 江阴市向阳科技有限公司 | Method for producing epoxy plasticizer using waste grease |
-
2008
- 2008-09-02 CN CN2008101195340A patent/CN101343380B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648237A (en) * | 2009-09-30 | 2012-08-22 | 陶氏环球技术有限责任公司 | Acetylated derivatives of castor oil and their blends with epoxidized fatty acid esters |
| CN105038261A (en) * | 2015-06-18 | 2015-11-11 | 张家港市大能塑料制品有限公司 | Environment-friendly plasticizer |
| CN109251444A (en) * | 2018-11-07 | 2019-01-22 | 长沙小如信息科技有限公司 | Plasticizer for polyvinyl chloride and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101343380B (en) | 2011-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101343380B (en) | Method for preparing elasticizer | |
| CN102924698A (en) | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate | |
| CN107188802A (en) | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type | |
| CN101811970B (en) | Production method of dioctyl terephthalate composite plasticizer | |
| CN111777510A (en) | Preparation method and application of plant oil-based environment-friendly plasticizer with high thermal stability | |
| CN101367731A (en) | C22 triacid triester elasticizer and method of preparing the same | |
| CN105085980A (en) | Synthesis of citric acid ether ester plasticizer | |
| CN110684139B (en) | Preparation method and application of tung oil-based polymer and preparation method of tung oil-based polymer derivative | |
| CN102559125B (en) | Degradable solvent free polyurethane adhesive and preparation and use method thereof | |
| CN107698449A (en) | A kind of synthetic method of the positive nonyl ester plasticiser of tri trimellitate | |
| CN102863879B (en) | Waterborne three-component polyester paint and preparation method thereof | |
| CN108822284B (en) | Method for preparing near-zero VOC alkyd resin by using illegal cooking oil and alkyd resin | |
| CN109970556A (en) | One vegetable oil chitin alcohol ether-ether and its preparation method and application | |
| CN111269113A (en) | Method for treating mixture containing long-chain dibasic acid, dibutyl long-chain dibasic acid mixture and application thereof | |
| CN114805928B (en) | Biological base plasticizer for metaphenylene | |
| CN103540203B (en) | Degradable multifunctional protective film | |
| CN101735052B (en) | Method for preparing dibutyl itaconate | |
| CN106317430A (en) | Preparation method of potato full-degradable plastic film | |
| CN112126121B (en) | Method for preparing cold-resistant and extraction-resistant rubber plasticizer by using unsaturated fatty acid methyl ester | |
| CN106750524B (en) | A kind of multiple-effect castor oil-base PVC liquid calcium zinc heat stabilizer and its preparation method and application | |
| CN105384630B (en) | Hexylene glycol ester of citric acid three and preparation method thereof | |
| DE102011084478A1 (en) | Preparing poly(vinyl ester-vinyl ether-vinyl alcohol-olefin) copolymer comprising e.g. olefin and vinyl alcohol monomer units, useful as packaging material, comprises radically copolymerizing monomers and carrying out alkaline hydrolysis | |
| CN114381080B (en) | Application of polyvinyl alcohol material, material for suction tube, preparation method of material and suction tube | |
| CN114805786B (en) | Tannin extract-based polyether polyol fatty acid ester plasticizer and preparation method and application thereof | |
| CN102703224A (en) | Method for preparing substance containing epoxyfatty acid low carbon alcohol ester plasticizer by palm oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |