CN105175697A - Preparation method of plant oil-based polyester plasticizer - Google Patents
Preparation method of plant oil-based polyester plasticizer Download PDFInfo
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- CN105175697A CN105175697A CN201510424900.3A CN201510424900A CN105175697A CN 105175697 A CN105175697 A CN 105175697A CN 201510424900 A CN201510424900 A CN 201510424900A CN 105175697 A CN105175697 A CN 105175697A
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Abstract
The invention relates to a preparation method of a plant oil-based polyester plasticizer. The plant oil-based polyester plasticizer is prepared from plant oil, glycerin, diacid or acid anhydride, and n-butanol or isooctyl alcohol or another micro-molecular monohydric alcohol. Compared with other polyester plasticizers, the plant oil-based polyester plasticizer has the advantages of renewable reaction raw materials, moderate viscosity, controllable molecule mass, good polyvinyl chloride plasticizing effect, and improvement of the thermal stability of polyvinyl chloride products.
Description
Technical field
The invention belongs to plasticizer technical field, be specifically related to a kind of preparation method of plant oil based polyester plasticizer.
Background technology
Softening agent is one of output and the maximum additives for plastics of consumption in the world, provide for the mankind play a part in high-quality plastics indispensable, softening agent is mainly based on adjacent benzoic ether series products for a long time, along with phthalic ester is more and more extensive in the application that food, medicine etc. are industrial, the toxicity of people to it is also more and more paid attention to.U.S. environment protection general bureau, according to the result of study of National Cancer Institute, has limited 6 kinds of adjacent benzene class softening agent and has used in environmental protection and the higher field of sanitary condition.Due to phthalate be applied to medicine equipment, toy for children, packaging material for food as polyvinyl chloride primary plasticizer time, easily ooze out from goods, serious threat brought to human health.Therefore, softening agent is towards high molecular, functionalization, nontoxic, eco-friendly future development, and thermotolerance and weather resistance be polyester plasticizer all well, and future market development prospect is wide.
Polyester plasticizer molecular weight is comparatively large, and in the course of processing, volatility is low, is not easily extracted out by water, oil and solvent, and transport property is little, high temperature resistant, goods can be made to keep preferable quality and work-ing life for a long time, thus reduce additives for plastics from goods, separate out the possibility that human body is worked the mischief.Polyester plasticizer is specially adapted to the covering with paint on steel, timber, fabric and PVC floor tile surface, to strengthen anti-pollution, wear-resistant, solvent resistant, water-fast extraction and to prevent water suction and expand.The synthesis of polyester plasticizer, generally at the temperature of about 200 DEG C, is formed through esterification, polycondensation by diprotic acid and dibasic alcohol.That the most frequently used is monounsaturated dicarboxylic acid (hexanodioic acid, sebacic acid, phthalic acid etc.) and C
2-C
4dibasic alcohol synthesis, charging capacity and the different end-capping reagent of employing of variation reaction can obtain different polyester products. and the main raw material diprotic acid of previous scholars synthesizing polyester softening agent, acid anhydrides and dibasic alcohol etc., all from fossil resource, do not meet the requirement of Sustainable development.Given this, the invention provides a kind of method using renewable resources vegetables oil substitute fossil fuels to prepare polyester plasticizer, polyester plasticizer prepared by the method, modest viscosity, molecular weight can control, and plasticization effect is good, can improve the thermostability of polrvinyl chloride product.
Summary of the invention
The technical problem solved: substitute petrochemical material synthesizing polyvinyl chloride polyester plasticizer to utilize renewable resources vegetables oil further.The invention provides a kind of preparation method of plant oil based polyester plasticizer, use the method to prepare and have modest viscosity, molecular weight can control, and plasticization effect is good, can improve the polyester plasticizer of the thermostability of polrvinyl chloride product.
Technical scheme: a kind of preparation method of plant oil based polyester plasticizer, comprises following two steps: (A) is at N
2in atmosphere, vegetables oil, glycerine and the first catalyzer temperature-elevating are carried out reaction 2-8h to 220-240 DEG C, vegetables oil and glycerine, according to molar ratio 1:2-2.5, obtain vegetables oil mono-glycerides intermediate; (B) by described intermediate under 180-240 DEG C of condition, reaction 6-12h is carried out with the second catalyzer, diprotic acid or acid anhydrides, monohydroxy-alcohol, the molar ratio that intermediate mixes with diprotic acid or acid anhydrides is 1:1, monohydroxy-alcohol consumption is the 0-30% of diprotic acid or acid anhydrides molar weight, obtains plant oil based polyester plasticizer.
Above-mentioned raw materials vegetables oil is the one in soya-bean oil, plam oil, sweet oil, rapeseed oil; Diprotic acid is the one in succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid; Acid anhydrides is the one in diacetyl oxide, Tetra hydro Phthalic anhydride; Monohydroxy-alcohol is the one in propyl carbinol, isooctyl alcohol.
The reaction of above-mentioned steps A is carried out under the effect of the first catalyzer, and described first catalyzer is sodium hydroxide or plumbous oxide, and catalyst levels is the 0.5%-1.5% of reactant total mass.
Above-mentioned steps B carries out under the second catalyst action, and described second catalyzer is tetrabutyl titanate, and catalyst levels is the 0.01%-0.05% of reactant total mass.
Steps A is specially: mixed according to molar ratio 1:2.5 with glycerine by vegetables oil, react in protective atmosphere, and the reaction times is 8h, obtains intermediate.
Step B is specially: mixed with diprotic acid or acid anhydrides by described intermediate, and molar ratio is 1:1, and monohydroxy-alcohol consumption is 30% of diprotic acid or acid anhydrides molar weight, and the reaction times is 8h.
Cool after above-mentioned polycondensation, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and obtain polyester product after dry 36h at vacuum tightness-0.1MPa, temperature are 60 DEG C.
Beneficial effect:
1) products material is mainly renewable resources vegetables oil, cheap and easy to get compared with petrochemical material, environment-protecting asepsis, biological degradability is good, the reproducible feature of raw material, product can play plasticization effect in polrvinyl chloride product, partly can replace adjacent benzene class softening agent, and improve the thermostability of plasticized polyvinyl chloride;
2) building-up process is simple, without poison gas release, is applicable to suitability for industrialized production, meets green and cleanly production technique.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of poly-sebacic acid soya-bean oil base binary alcohol esters and poly-Tetra hydro Phthalic anhydride soya-bean oil base binary alcohol esters.The methyl of poly-sebacic acid soya-bean oil base binary alcohol esters length fatty acids chain and methylene group absorption peak are at 2852.96cm
-1and 2922.54cm
-1near, at 1739.28cm
-1there is stronger carbonyl absorption peak at place, illustrates that stronger carbonyl group exists, at 3467.81cm
-1there is more weak absorption peak, illustrate that this soya-bean oil polyester is by hydroxy-end capped.As can be seen from the infrared spectrogram of poly-Tetra hydro Phthalic anhydride soya-bean oil base binary alcohol esters, 1736.04cm
-1there is stronger carbonyl absorption peak at place, illustrates that stronger carbonyl group exists, at 3408.78cm
-1there is more weak absorption peak, use isooctyl alcohol to be end-capping reagent in an experiment, illustrate that this soya-bean oil polyester is by hydroxy-end capped.1736.04cm
-1for the ester group infrared absorption peak of poly-Tetra hydro Phthalic anhydride soya-bean oil base binary alcohol esters, 1580.64cm
-1for the charateristic avsorption band of phenyl group.
Fig. 2 is the thermal stability analysis figure of polyvinyl chloride test piece.As seen from the figure, the PVC test piece extension thermal degradation temperature having added poly-sebacic acid soya-bean oil base binary alcohol esters and poly-Tetra hydro Phthalic anhydride soya-bean oil base binary alcohol esters softening agent is respectively 257 DEG C and 268 DEG C, and the extension thermal degradation temperature of the PVC test piece of traditional plasticizer phthalic acid dioctyl ester plasticising is 251 DEG C.
Embodiment
Be described further with specific embodiment below: in the present invention, all raw materials are all commercially available, if without specializing in following examples, be all mass parts.
Embodiment 1
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds 440 mass parts soya-bean oil in batches, react 6h at 230 DEG C after, reaction vessel is placed in frozen water cool to room temperature and obtains soya-bean oil Tegin 55G.The soya-bean oil Tegin 55G of 290 mass parts and the sebacic acid of 202 mass parts are placed in reaction vessel, the tetrabutyl titanate adding 0.15 mass parts is catalyzer, and nitrogen atmosphere, keeps 20min at 150 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 6h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and at vacuum, temperature are 60 DEG C, after dry 36h, obtain poly-sebacic acid soya-bean oil base binary alcohol esters polyester product.Final acid number is 1.65mgKOHg
-1, esterification yield is 98.37%, and color and luster is clear yellow, and viscosity is 2.6Pas, and molecular mass is 21339g/mol, and distribution coefficient is 1.57.
Embodiment 2
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds 440 mass parts soya-bean oil in batches, react 6h at 230 DEG C after, reaction vessel is placed in frozen water cool to room temperature and obtains soya-bean oil Tegin 55G.The soya-bean oil Tegin 55G of 290 mass parts and the hexanodioic acid of 146 mass parts are placed in reaction vessel, adding 0.13 mass parts tetrabutyl titanate is catalyzer, and nitrogen atmosphere, keeps 20min at 150 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 6h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and at vacuum, temperature are 60 DEG C, after dry 36h, obtain poly-hexanodioic acid soya-bean oil base binary alcohol esters polyester product.Final acid number is 1.68mgKOHg
-1, esterification yield is 98.68%, and color and luster is clear yellow, and viscosity is 2.6Pas, and molecular mass is 19136g/mol, and distribution coefficient is 1.53.
Embodiment 3
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds 440 mass parts soya-bean oil in batches, react 6h at 230 DEG C after, reaction vessel is placed in frozen water cool to room temperature and obtains soya-bean oil Tegin 55G.By the soya-bean oil Tegin 55G of 290 mass parts and 132 mass parts pentanedioic acid equimolar amounts as in reaction vessel, the tetrabutyl titanate adding 0.13 mass parts is catalyzer, and nitrogen atmosphere, keeps 20min at 150 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 6h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and at vacuum, temperature are 60 DEG C, after dry 36h, obtain poly-pentanedioic acid soya-bean oil base binary alcohol esters polyester product.Whole acid number is 1.21mgKOHg
-1, esterification yield is 99.12%, and color and luster is clear yellow, and viscosity is 2.6Pas, and molecular mass is 18364g/mol, and distribution coefficient is 1.31.
Embodiment 4
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds 440 mass parts soya-bean oil in batches, react 6h at 230 DEG C after, reaction vessel is placed in frozen water cool to room temperature and obtains soya-bean oil Tegin 55G.The soya-bean oil Tegin 55G of 290 mass parts and 98 mass parts maleic anhydride equimolar amounts are placed in reaction vessel, the tetrabutyl titanate adding 0.12 mass parts is the isooctyl alcohol of catalyzer and 23 mass parts is end-capping reagent, nitrogen atmosphere, 20min is kept at 80 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 10h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, vacuum tightness-0.1MPa, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and obtain polymaleic anhydride soya-bean oil base binary alcohol esters polyester product after dry 36h at vacuum (vacuum tightness-0.1MPa), temperature are 60 DEG C.Final acid number is 0.96mgKOHg
-1, esterification yield is 97.31%, and color and luster is clear yellow, and institute's viscosity is 2.7Pas, and molecular mass is 3530g/mol, and dispersion coefficient is 2.10.
Embodiment 5
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds 440 mass parts soya-bean oil in batches, react 6h at 230 DEG C after, reaction vessel is placed in frozen water cool to room temperature and obtains soya-bean oil Tegin 55G.The soya-bean oil Tegin 55G of 290 mass parts and the Tetra hydro Phthalic anhydride of 148 mass parts are placed in reaction vessel, the tetrabutyl titanate adding 0.13 mass parts is the isooctyl alcohol of catalyzer and 23 mass parts is end-capping reagent, 20min is kept at 150 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 6h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, removing reaction process generate small-molecule substance.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and at vacuum, temperature are 60 DEG C, after dry 36h, obtain poly-phthalic acid soya-bean oil base binary alcohol esters polyester product.Final acid number is 1.72mgKOHg
-1, esterification yield is 99.17%, and color and luster is clear yellow, and products obtained therefrom viscosity is 3.2Pas, and molecular mass is 3812g/mol, and dispersion coefficient is 1.52.
Embodiment 6
180 mass parts glycerine are kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the plumbous oxide adding 0.6 mass parts is catalyzer, adds 440 parts of plam oils in batches, react 3.5h at 230 DEG C after, reaction vessel is placed in frozen water cooling and obtains plam oil Tegin 55G.The plam oil Tegin 55G of 290 mass parts and 98 mass parts maleic anhydrides are placed in reaction vessel, the tetrabutyl titanate adding 0.12 mass parts is the isooctyl alcohol of catalyzer and 23 mass parts is end-capping reagent, nitrogen atmosphere, 20min is kept at 80 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 12h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, vacuum tightness-0.1MPa, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and obtain polymaleic anhydride palm oil-base binary alcohol esters polyester product after dry 36h at vacuum (vacuum tightness-0.1MPa), temperature are 60 DEG C.The whole acid number of products obtained therefrom is 1.78mgKOHg
-1, esterification yield is 97.32%, and color and luster is brown, and viscosity is 2.6Pas, and molecular mass is 3101g/mol, and dispersion coefficient is 1.81.
Embodiment 7
The glycerine of 180 mass parts is kept 2h under 220 DEG C and nitrogen atmosphere, remove moisture, the sodium hydroxide adding 0.6 mass parts is catalyzer, adds the plam oil of 440 mass parts in batches, react 3.5h at 230 DEG C after, reaction vessel is placed in frozen water cooling and obtains plam oil Tegin 55G.The plam oil Tegin 55G of 290 mass parts and the Tetra hydro Phthalic anhydride of 148 mass parts are placed in reaction vessel, the tetrabutyl titanate adding 0.13 mass parts is the isooctyl alcohol of catalyzer and 23 mass parts is end-capping reagent, nitrogen atmosphere, 20min is kept at 80 DEG C, until reactant all melts, start agitator, be heated to 230 DEG C, keep 12h, after convert Depressor response device to, at 230 DEG C, vacuumize 2h, vacuum tightness-0.1MPa, the small-molecule substance that removing reaction process generates, between the reaction period, METHOD FOR CONTINUOUS DETERMINATION acid number judges level of response.After cooling, reaction product is dissolved in chloroform and deionized water, repeatedly dissolves and wash, and obtain poly-Tetra hydro Phthalic anhydride palm oil-base binary alcohol esters polyester product after dry 36h at vacuum (vacuum tightness-0.1MPa), temperature are 60 DEG C.The whole acid number of products obtained therefrom is 1.81mgKOHg
-1, esterification yield is 98.02%, and color and luster is brown, and viscosity is 2.8Pas, and molecular mass is 3130g/mol, and dispersion coefficient is 1.76.
According to formula shown in expression, use torque rheometer thermoplastic, make dumbbell shape batten in micro injection molding machine, use universal tensile testing machine to test according to GB1040-2006, stretching experiment test data is listed in table 2.After the polyester plasticizer that in table 2, data presentation is synthesized along with phthalate ester moieties replaces, the mechanical property of polyvinyl chloride blend decreases, and illustrates that the polyester plasticizer of synthesis can as the secondary softening agent use of polyvinyl chloride.
The polychloroethylene blended formula of table 1
Table 2 stretching experiment test chart
Claims (7)
1. a preparation method for plant oil based polyester plasticizer, is characterized in that comprising following two steps:
A) at N
2in atmosphere, vegetables oil, glycerine and the first catalyzer temperature-elevating are carried out reaction 2-8h to 220-240 DEG C, vegetables oil and glycerine, according to molar ratio 1:2-2.5, obtain vegetables oil mono-glycerides intermediate;
B) by described intermediate under 180-240 DEG C of condition, reaction 6-12h is carried out with the second catalyzer, diprotic acid or acid anhydrides, monohydroxy-alcohol, the molar ratio that intermediate mixes with diprotic acid or acid anhydrides is 1:1, monohydroxy-alcohol consumption is the 0-30% of diprotic acid or acid anhydrides molar weight, obtains plant oil based polyester plasticizer.
2. the preparation method of plant oil based polyester plasticizer according to claim 1, is characterized in that: described material plant oil is the one in soya-bean oil, plam oil, sweet oil, rapeseed oil; Diprotic acid is the one in succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid; Acid anhydrides is the one in diacetyl oxide, Tetra hydro Phthalic anhydride; Monohydroxy-alcohol is the one in propyl carbinol, isooctyl alcohol.
3. the preparation method of plant oil based polyester plasticizer according to claim 1, it is characterized in that: the reaction of described steps A is carried out under the effect of the first catalyzer, described first catalyzer is sodium hydroxide or plumbous oxide, and catalyst levels is the 0.5%-1.5% of reactant total mass.
4. the preparation method of plant oil based polyester plasticizer according to claim 1, it is characterized in that: described step B carries out under the second catalyst action, described second catalyzer is tetrabutyl titanate, and catalyst levels is the 0.01%-0.05% of reactant total mass.
5. the preparation method of plant oil based polyester plasticizer according to claim 1, it is characterized in that: steps A is specially: mixed according to molar ratio 1:2.5 with glycerine by vegetables oil, react in protective atmosphere, the reaction times is 8h, obtains intermediate.
6. the preparation method of plant oil based polyester plasticizer according to claim 1, it is characterized in that: step B is specially: described intermediate is mixed with diprotic acid or acid anhydrides, molar ratio is 1:1, and monohydroxy-alcohol consumption is 30% of diprotic acid or acid anhydrides molar weight, and the reaction times is 8h.
7. the preparation method of plant oil based polyester plasticizer according to claim 6, it is characterized in that: cool after polycondensation, reaction product is dissolved in chloroform and deionized water, repeatedly dissolve and wash, and obtain polyester product after dry 36h at vacuum tightness-0.1MPa, temperature are 60 DEG C.
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Cited By (5)
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| CN107141460A (en) * | 2017-06-12 | 2017-09-08 | 浙江大学 | The synthetic method of one vegetable oil based thermoplastic polyester |
| CN108047491A (en) * | 2018-01-25 | 2018-05-18 | 广东达华生态科技有限公司 | A kind of new PVC plasticizer and preparation method thereof |
| CN109836563A (en) * | 2017-11-29 | 2019-06-04 | 北京旭阳科技有限公司 | A kind of preparation method of the unsaturated polyester resin containing glycerol monomethyl ether unit |
| WO2022017639A1 (en) | 2020-07-20 | 2022-01-27 | Bio Bond Aps | Bio-based plasticiser for resins and blends containing said plasticiser |
| WO2024067892A3 (en) * | 2022-09-30 | 2024-05-30 | 明达光电(厦门)有限公司 | Composite vegetable oil plasticizer, and preparation method therefor and use thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141460A (en) * | 2017-06-12 | 2017-09-08 | 浙江大学 | The synthetic method of one vegetable oil based thermoplastic polyester |
| CN107141460B (en) * | 2017-06-12 | 2019-03-19 | 浙江大学 | The synthetic method of one vegetable oil based thermoplastic polyester |
| CN109836563A (en) * | 2017-11-29 | 2019-06-04 | 北京旭阳科技有限公司 | A kind of preparation method of the unsaturated polyester resin containing glycerol monomethyl ether unit |
| CN109836563B (en) * | 2017-11-29 | 2021-02-19 | 北京旭阳科技有限公司 | Preparation method of unsaturated polyester resin containing glycerol monomethyl ether unit |
| CN108047491A (en) * | 2018-01-25 | 2018-05-18 | 广东达华生态科技有限公司 | A kind of new PVC plasticizer and preparation method thereof |
| WO2022017639A1 (en) | 2020-07-20 | 2022-01-27 | Bio Bond Aps | Bio-based plasticiser for resins and blends containing said plasticiser |
| EP3992227A1 (en) | 2020-07-20 | 2022-05-04 | Bio Bond ApS | Bio-based plasticiser for resins and blends containing said plasticiser |
| WO2024067892A3 (en) * | 2022-09-30 | 2024-05-30 | 明达光电(厦门)有限公司 | Composite vegetable oil plasticizer, and preparation method therefor and use thereof |
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