CN1015546B - Plasticizer - Google Patents
PlasticizerInfo
- Publication number
- CN1015546B CN1015546B CN 88102691 CN88102691A CN1015546B CN 1015546 B CN1015546 B CN 1015546B CN 88102691 CN88102691 CN 88102691 CN 88102691 A CN88102691 A CN 88102691A CN 1015546 B CN1015546 B CN 1015546B
- Authority
- CN
- China
- Prior art keywords
- ecs
- plasticizer
- acid
- citrate
- softening agent
- 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.)
- Expired
Links
Abstract
The present invention relates to an ECS plasticizer which belongs to diad citrate ester. The ECS plasticizer is mainly applied to polyvinyl chloride resin for making non-toxic PVC products and is applied to food packaging material, medical article material, water supply pipes for building, etc., and is also a non-toxic plasticizer or a softener for cellulose resin and synthetic rubber. Using citric acid, diethylene glycol, butanol and propylene oxide as raw materials, the ECS plasticizer is formed by multi-step condensation. The ECS plasticizer has plenty of advantages, so that when the ECS plasticizer is used in PVC products, the performances (mechanical processing performance, heat resistance performance, cold resistance performance, plasticization performance, etc.) of the PVC products can reach the international standard, and the ECS plasticizer is a plasticiser with the performances of a secondary plasticizer and a primary plasticizer.
Description
The softening agent ECS of the present invention's preparation, full name is: double citric acid (glycol ether, four butanols) ester or double citric acid (bis-epoxy propane glycol ether) ester are to belong to dual tricaprylyl citrate.Be mainly used in polyvinyl chloride (PVC) RESINS, make nontoxic PVC product, be used for packaging material for food, medical article material, the upper hoses of building trade etc. also are the elastomeric non-toxic plasticizer of celluosic resin, tenderizer.
Along with the needs in macromolecular material industrial expansion and market, must develop the production of non-toxic plasticizer, to adapt to the demand of each side, the production of citrate plasticizer yet there are no any report in China, abroad begins to use in the sixties.According to document (Deutsches Reichs-Patent 1200528 report, synthetic route of external compound and raw material are as follows:
Its raw material is: citric acid, unit alcohol (butanols etc.), and hexanodioic acid, pentanedioic acid, sebacic acid etc. and phosphorus trichloride.
Synthetic route is the first step elder generation synthesizing citric acid ester substantially.
Citric acid and unit alcohol react under acid catalysis and form ester:
Make diprotic acid form diacid chloride simultaneously
The second step citrate and diacid chloride reaction form dual citrate
N is generally between 4-8
Need to use expensive diprotic acid and phosphorus trichloride (or phosphorus oxychloride) in this synthetic route, diprotic acid-as hexanodioic acid, sebacic acid etc., raw material is difficult for obtaining in China, in making the diacid chloride process, use the phosphorus trichloride isoreactivity can be extremely active, the requirement of working condition than higher, is needed special anticorrosion equipment, and the labor condition in workshop is worsened, these conditions are not that general plasticising factory can solve.
And the working condition of softening agent ECS of the present invention can be simplified greatly.General chemical industry equipment just can be produced, and just general plasticising factory does not need specific installation and condition just passable.
The preparation method of dual citrate softening agent ECS of the present invention:
Two-fold citric acid softening agent ECS is double citric acid (glycol ether, four butanols) ester or double citric acid (bis-epoxy propane glycol ether, four butanols) ester, and their molecular formula is respectively:
They are raw materials used to be citric acid, butanols, glycol ether (glycol ether), propylene oxide, diacetyl oxide.
(ⅰ) citrate and butanols get acid ester earlier with 1: 2 mole ratio.
Under the sulfuric acid catalysis effect, sulfuric acid consumption 0.3-1%.
(ⅱ) glycol ether and propylene oxide reaction form ether alcohol.
This is reflected at sulphur phosphorus mixing acid is catalyzer, under the 1-8 normal atmosphere.
(ⅲ) acid citrate and ether alcohol the reaction get final product ECS.
The mole ratio of acid citrate and ether alcohol is 2: 1.
If with 3: 2 proportionings, the more triple citrates of ECS of macromolecule will be obtained.
(ⅳ) acetylizad ECS
The two ends of ECS molecule also have two hydroxyls, get acetylizad ECS through the diacetyl oxide acetylize
Dual citrate of the present invention is compared with the dual citrate of foreign literature report:
Identical point:
(ⅰ) main raw material citric acid and unit alcohol.
(ⅱ) product all is the dual citrate of macromolecule.
(ⅲ) product structure is similar, performance classes seemingly, purposes is also approximate.
Institute's difference:
(ⅰ) part main raw material difference, the production cost difference.
One is to use diprotic acid: phosphorus trichloride (or phosphorus oxychloride)
One is with glycol ether, propylene oxide
(ⅱ) difference of working condition.
Need are with special anticorrosion equipment, and facility investment is bigger
The general chemical industry equipment of usefulness just can be produced
When making diacid chloride, environment is easily polluted, labor condition is poor.
Diacid chloride, phosphorus trichloride in humid atmosphere very easily hydrolysis emit hydrogen chloride gas, production need be carried out under dry airy condition.
(ⅲ) difference of economic benefit.
Because the difference of main raw material, the synthetic route difference, the production cost difference, working condition required equipment difference, the long and causes the difference of economic benefit.
The situation of China, diprotic acid such as hexanodioic acid, sebacic acid extremely lack, and be undersupplied products, and glycol ether are oversupplied products, are the by products of producing ethylene glycol, and drug on the market, price is very cheap.Propylene oxide is raw material with the propylene, and propylene is by the petroleum cracking product, and it is abundanter to originate.
By service condition, softening agent plasticizing efficiency height of the present invention not only can replace extender plasticizer, but also can the instead of part primary plasticizer.Good processability is adapted to the big production of industry.
Claims (4)
1, a kind of preparation method of dual citrate ECS softening agent is characterized in that (i) citric acid and butanols get acid ester earlier with 1: 2 mole ratio; (ii) glycol ether and propylene oxide reaction form ether alcohol; The reaction of (iii) acid citrate and ether alcohol get final product dihydroxyl dual citrate ECS; (iv) dihydroxyl dual citrate and acetic anhydride get final product acetylizad ECS.
2, the preparation method of ECS softening agent according to claim 1 is characterized in that (ⅰ) citric acid and butanols react under sulfuric acid is made catalyst action, the sulfuric acid consumption is 0.3-1%.
3, the preparation method of ECS softening agent according to claim 1 is characterized in that (ⅱ)-diglycol ethylene and propylene oxide are at 1-8 normal atmosphere, and sulphur phosphorus mixing acid is to react under the catalyst action.
4, the preparation method of ECS softening agent according to claim 1, it is characterized in that (ⅱ) glycol ether and propylene oxide are 1 with mole ratio: 2.05-1: 2.5 react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102691 CN1015546B (en) | 1988-05-06 | 1988-05-06 | Plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102691 CN1015546B (en) | 1988-05-06 | 1988-05-06 | Plasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037350A CN1037350A (en) | 1989-11-22 |
| CN1015546B true CN1015546B (en) | 1992-02-19 |
Family
ID=4832263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102691 Expired CN1015546B (en) | 1988-05-06 | 1988-05-06 | Plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015546B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7297738B2 (en) * | 2001-09-25 | 2007-11-20 | Exxonmobil Chemical Patents Inc. | Plasticized polyvinyl chloride |
| DE102009028975A1 (en) * | 2009-08-28 | 2011-03-03 | Evonik Oxeno Gmbh | Ester derivatives of 2,5-furandicarboxylic acid and their use as plasticizers |
| CN105085980A (en) * | 2014-05-09 | 2015-11-25 | 天津科技大学 | Synthesis of citric acid ether ester plasticizer |
| CN108948426A (en) * | 2018-07-05 | 2018-12-07 | 胡果青 | A kind of preparation method of plastic plasticizer |
-
1988
- 1988-05-06 CN CN 88102691 patent/CN1015546B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037350A (en) | 1989-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832801B (en) | A kind of lignin modification PBAT biodegradable plastic and preparation method thereof | |
| EP1373395B1 (en) | Process for preparing a stabilized polyester | |
| CN1113748C (en) | Composite layered products contg. more than one layer | |
| CN106589854B (en) | A kind of full biology base PBSA biodegradable plastics of lignin modification and preparation method thereof | |
| EP2984064B1 (en) | Process of producing 1,4-butanediol | |
| CN101679708A (en) | Composition of terephthalic acid esters for polymer resin and method of manufacturing the same | |
| CN1015546B (en) | Plasticizer | |
| CN111057284A (en) | Reinforced HDPE double-wall corrugated pipe and preparation method thereof | |
| CN1180007C (en) | Neopentylglycol ester based plasticizer composition for polyvinyl chloride resin and method of preparation thereof | |
| CN113549323A (en) | High-strength high-flow low-warpage long glass fiber reinforced polyamide composite material, and preparation method and application thereof | |
| CN108948682A (en) | A kind of lignin modification PBAT/PLA composite film material and preparation method thereof | |
| EP0069475A2 (en) | Process for producing aliphatic copolyesteramide and tube moulded therefrom | |
| CN106479008B (en) | A kind of high-performance chemical pump rubber packing material | |
| EP1414883B1 (en) | Amorphous copolyesters | |
| CN101327625A (en) | PVC external lubricant | |
| CN111117223A (en) | Nylon material for automobile bearing and preparation method thereof | |
| CN1472254A (en) | Fibreglass reinforced polyester composite material and preparing method thereof | |
| CN101215372A (en) | Preparation method of polyesters for tyre cord yarn | |
| CN1546570A (en) | Composite material of fibrous nanometer clay and high viscosity polyamide | |
| KR20120005254A (en) | Preparing method of recycled polyamide66 resin | |
| CN1425703A (en) | Process for preparing polyester | |
| CN101173063A (en) | Multifunctional rubber chemicals and method for producing the same | |
| CN100460457C (en) | Manufacturing method of high baffer modified polyester | |
| CN1263122A (en) | Preparation method of high concentration phosphorous copolyester | |
| CN1306020A (en) | Process for preparing high-concentration phosphorus-contained copolyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |