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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- 229920000728 polyester Polymers 0.000 title claims abstract description 39
- 239000004014 plasticizer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010773 plant oil Substances 0.000 title description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 23
- 235000011187 glycerol Nutrition 0.000 claims abstract description 14
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract 16
- 239000008158 vegetable oil Substances 0.000 claims abstract 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims 1
- 235000019482 Palm oil Nutrition 0.000 claims 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 235000011037 adipic acid Nutrition 0.000 claims 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000004006 olive oil Substances 0.000 claims 1
- 235000008390 olive oil Nutrition 0.000 claims 1
- 239000002540 palm oil Substances 0.000 claims 1
- 235000012424 soybean oil Nutrition 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract description 15
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 11
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 47
- 235000019198 oils Nutrition 0.000 description 47
- 244000068988 Glycine max Species 0.000 description 30
- 235000010469 Glycine max Nutrition 0.000 description 30
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 8
- 239000004902 Softening Agent Substances 0.000 description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
- 150000007520 diprotic acids Chemical class 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 235000013311 vegetables Nutrition 0.000 description 8
- 239000002932 luster Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 timber Substances 0.000 description 2
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical group CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical group 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种植物油基聚酯增塑剂的制备方法，其以植物油、甘油、二元酸或酸酐、正丁醇或异辛醇等小分子一元醇为原料制备而成，所述植物油基高分子聚酯增塑剂相对其他聚酯增塑剂有反应原料可再生，粘度适中，分子质量可控，对聚氯乙烯增塑效果良好，能够提高聚氯乙烯制品的热稳定性等优点。
A preparation method of a vegetable oil-based polyester plasticizer, which is prepared from small molecular monohydric alcohols such as vegetable oil, glycerin, dibasic acid or anhydride, n-butanol or isooctyl alcohol, and the vegetable oil-based polymer polymer Compared with other polyester plasticizers, ester plasticizers have the advantages of renewable raw materials, moderate viscosity, controllable molecular weight, good plasticizing effect on polyvinyl chloride, and can improve 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
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| CN118667134A (en) * | 2024-06-11 | 2024-09-20 | 广东华博润材料科技有限公司 | Bio-based plasticizer and preparation method and application thereof |
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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 |
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| 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 |
| CN118496628A (en) * | 2024-05-17 | 2024-08-16 | 广州纽力斯新材料科技有限公司 | Modified polyester for improving toughness, temperature resistance and oil resistance of plastic and preparation method thereof |
| CN118667134A (en) * | 2024-06-11 | 2024-09-20 | 广东华博润材料科技有限公司 | Bio-based plasticizer and preparation method and application thereof |
| CN118667134B (en) * | 2024-06-11 | 2025-02-25 | 广东华博润材料科技有限公司 | A bio-based plasticizer and its preparation method and application |
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