CN109880532A - A kind of dimeric dibasic acid and its preparation method and application - Google Patents
A kind of dimeric dibasic acid and its preparation method and application Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 35
- 239000002383 tung oil Substances 0.000 claims abstract description 26
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims abstract description 21
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000004831 Hot glue Substances 0.000 claims abstract description 3
- 239000004952 Polyamide Substances 0.000 claims abstract description 3
- 239000010687 lubricating oil Substances 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000010926 purge Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 244000055346 Paulownia Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of dimeric dibasic acid and its preparation method and application, the molecular formula of dimeric dibasic acid is C34H58(COOH)2, wherein mononuclear type dimerization acid content is greater than 70%.It is to be prepared using tung oil or eleostearic acid as raw material, preparation process is simple, and environmental protection and economy is good the present invention also provides the preparation method of above-mentioned dimeric dibasic acid.Prepared dimeric dibasic acid can be used for preparing polyamide, hot melt adhesive, lubricating oil etc., and application range is wide.
Description
Technical field
The invention belongs to polymer arts, and in particular to a kind of dimeric dibasic acid and its preparation method and application.
Background technique
Dimeric dibasic acid is because, containing there are two gaining the name due to carboxylic acid group, referring mainly to C18 unsaturated fatty acid in certain item in its molecule
Under part, generate according to Diels-Alder reaction with C36 dimeric dibasic acid as main component.According to reaction mechanism, dimeric dibasic acid it is basic
Structure is roughly divided into three classes: mononuclear type, double ring type and non-ring-like.Currently, commodity dimeric dibasic acid is usually three kinds of isomer groups
At mixture.
The molecular weight of dimeric dibasic acid is moderate, unique structure, the flexible carbochain of existing length in molecule, and the ring with relative stiffness
Shape structure not only has polarity and non-polar group concurrently, also has the active reactive groups of properties such as carbonyl and double bond.These are solely
Special molecular structure makes it have unique physicochemical properties and extensive use, can be used for synthesis of polyurethane resin, petroleum adds
Corrosion inhibitor, lubricant, fuel additive, coating and plant oil stabilizer etc. in construction equipment.
The primary raw material of production dimeric dibasic acid is tall oil acid, cotton oil acid, soybean oleic acid etc. at present, and main component is sub- oil
Acid and oleic acid.The production technology of dimeric dibasic acid is mainly clay catalytic method or other catalyst methods, wherein clay catalytic method
It is the dimeric dibasic acid synthetic method being widely used at present.The performance of the dimeric dibasic acid of both techniques production is essentially identical.
Lu Xianghong is using oleic acid as raw material, in normal pressure, nitrogen protection, 240 DEG C of reaction temperature, reaction time 6h, atlapulgite
Dosage be oleic acid 12% (w), LiCl dosage be oleic acid 1.2% (w) under conditions of, the yield of dimeric dibasic acid is 34.6%(petroleum
Work, 2015,44 (4): 483-488).
WO 00/75252 discloses a kind of synthetic method of dimeric dibasic acid, and using C18 fatty acid as raw material, specific ingredient is such as
Under, 0.14% C14、6.97% C16、0.27% C16:1、3.22% C18、49.71% C18:1、28.56% C18:2、7.34%C18:3、
0.56% C20、1.15% C20:1、0.29%C22And 0.18%C22:1, calcium-base bentonite dosage is 4.5%, LiCO of raw material3Dosage is
The 0.07% of raw material, water consumption be raw material 1.0%, nitrogen protection, 254 DEG C of reaction temperature, reaction time 4h, reaction system highest
Pressure 219psig, reaction system dimerization acid content are 50.5%.
CN104804782A discloses a kind of synthetic method of dimeric dibasic acid, utilizes the fatty acid mixed prepared by sunflower oil
For raw material, 12% atlapulgite, 1% LiCO are added3, nitrogen purging protection, 240 DEG C of heating temperature, reaction time 6h, after
After continuous processing, the yield of dimeric dibasic acid is 67.6%.
In the above-mentioned methods, the synthesis of dimeric dibasic acid is required to add a large amount of catalyst or/and catalyst aid, and used urges
Agent is powdery, subsequent to isolate and purify higher cost, and product is lost in separation process, and it is dirty to will cause certain environment
Dye.It is general to be not less than 240 DEG C in addition, polymeric reaction temperature is higher, and part reaction process need it is with pressure, to equipment requirement compared with
It is high.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of dimeric dibasic acids and its preparation method and application.Of the invention
Dimeric dibasic acid is prepared using tung oil or eleostearic acid as raw material, and preparation process is simple, and environmental protection and economy is good, and application range is wide.
A kind of dimeric dibasic acid provided by the invention is prepared using tung oil or eleostearic acid as raw material, and the molecular formula of dimeric dibasic acid is
C34H58(COOH)2, wherein mononuclear type dimerization acid content is greater than 70%.
The synthetic method of dimeric dibasic acid provided by the invention is using eleostearic acid as raw material, and nitrogen purges simultaneously for stirring, is warming up to
180-230 DEG C of reaction obtains main C containing dimeric dibasic acid after the reaction was completed34H58(COOH)2Product.
The eleostearic acid can be using commodity eleostearic acid or self-control eleostearic acid.The speed of agitator is 50-500rpm, excellent
Select 200-400rpm.The nitrogen purge time is 1-30min, preferably 20-30min.The reaction temperature is 180-230 DEG C,
It is preferred that 200-220 DEG C；Reaction time is 2-7h, preferably 3-5h.It is cooled down, is generally cooled to room temperature after the reaction was completed, is i.e. 10-
40℃。
It is provided by the invention another kind dimeric dibasic acid synthetic method, be using tung oil as raw material, in the presence of catalyst, water,
Nitrogen purges simultaneously for stirring, is warming up to 170-220 DEG C of reaction, obtains main C containing dimeric dibasic acid after the reaction was completed34H58(COOH)2's
Product.
It is mainly eleostearic acid glyceryl ester in the tung oil, it can be using commodity tung oil or self-control tung oil.Described
Catalyst is quaternary ammonium salt catalyst, such as can be tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, three pungent
Methyl ammonium, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride etc.
One or more of, preferred dodecyl trimethyl ammonium bromide.The additive amount of catalyst is the 5 ‰ -5% of tung oil quality, preferably
1%-3%.The additive amount of the water is the volume ratio 1:1-6:1 for making water and tung oil, preferably 3:1-4:1.The stirring turns
Speed is 50-500rpm, preferably 200-400rpm.The nitrogen purge time is 1-30min, preferably 20-30min.It is described
Reaction temperature be 170-220 DEG C, preferably 200-210 DEG C；Reaction time is 2-7h, preferably 3-5h.It carries out after the reaction was completed cold
But, it is generally cooled to room temperature, i.e., 10-40 DEG C.Product carries out settle and separate after will be cooling, and supernatant liquid is dimerization acid product.Again
Water is distilled off in lower liquid and obtains glycerol production.
The application of synthesis of dimmer acid of the present invention can be used for preparing polyamide, hot melt adhesive, lubricating oil etc., or pass through
After distillation purification, in the field high to dimeric dibasic acid purity requirement.
Compared with prior art, the invention has the following advantages that
(1) dimeric dibasic acid is prepared using tung oil or eleostearic acid as raw material, the molecular formula of dimeric dibasic acid is C34H58(COOH)2, wherein mononuclear type
Dimerization acid content is greater than 70%.It is simple with preparation process, the advantages that environmental protection and economy is good, and application range is wide.
(2) using eleostearic acid as Material synthesis dimeric dibasic acid, also as parent's conjugation two while eleostearic acid is as conjugated diene body
Alkene body is not needed using catalyst in synthesis process, and no subsequent catalyst handles problem, dimeric dibasic acid high income, good product quality.
(3) using tung oil as raw material, in neighbour's circle water, one-step catalytic synthesis of dimmer acid, while by-product glycerol, have two
The features such as polyacids and yield of glycerin height, good product quality.
(4) reaction temperature of synthesis process is relatively low, and reaction process is not with pressure, requires consersion unit low.
Specific embodiment
The dimeric dibasic acid and its synthetic method and effect that the present invention synthesizes are further illustrated below by embodiment.Embodiment
Implemented under the premise of the technical scheme of the present invention, the detailed implementation method and specific operation process are given, but this
The protection scope of invention is not limited to the following embodiments.
Experimental method in following embodiment is unless otherwise specified conventional method in that art.Institute in following embodiments
Experimental material is commercially available from routine biochemistry reagent shop unless otherwise specified.
Dimeric dibasic acid, trimerization acid content are measured using GPC in sample, specific chromatographic condition are as follows: Shodex KF-801 gel color
Spectrum column, 35 DEG C of column temperature, mobile phase tetrahydrofuran, flow velocity 1mL/min, Composition distribution, 40 DEG C of detector temperature, sample volume
50mL。
Embodiment 1
Using commodity eleostearic acid (being purchased from Anhui Rui Fen get grease deep processing Co., Ltd, model: T160).Take 100g commodity tung oil
Sour T160 is placed in 250mL four-hole boiling flask, and nitrogen purges 30min, stirring rate 300rpm, is warming up to 220 DEG C of reaction 4h, is stopped
It only heats, natural cooling obtains dimerization acid product.It is measured through GPC, dimerization acid content is 40.62% in product, wherein mononuclear type two
Polyacids content is 83%.
Embodiment 2
Using commodity eleostearic acid (being purchased from Anhui Rui Fen get grease deep processing Co., Ltd, model: T155).Take 100 grams of commodity paulownias
Oleic acid T155 is placed in 250mL four-hole boiling flask, and nitrogen purges 30min, stirring rate 300rpm, is warming up to 220 DEG C of reaction 4h,
Stop heating, natural cooling obtains dimerization acid product.It is measured through GPC, dimerization acid content is 45.97% in product, wherein mononuclear type
Dimerization acid content is 92%.
Embodiment 3
Commodity eleostearic acid 100g same as Example 1 is taken to be placed in 250mL four-hole boiling flask, nitrogen purges 20min, stirring speed
Rate 400rpm is warming up to 230 DEG C of reaction 3h, stops heating, and natural cooling obtains dimerization acid product.It is measured through GPC, two in product
Polyacids content is 40.12%, and wherein mononuclear type dimerization acid content is 77%.
Embodiment 4
Commodity eleostearic acid 100g same as Example 1 is taken to be placed in 250mL four-hole boiling flask, nitrogen purges 10min, stirring speed
Rate 500rpm is warming up to 180 DEG C of reaction 7h, stops heating, obtains dimerization acid product from cooling.It is measured through GPC, dimerization in product
Acid content is 42.16%, and wherein mononuclear type dimerization acid content is 80%.
Embodiment 5
Using commodity tung oil (being purchased from Fujian gold forest industry limited liability company).It takes 50mL commodity tung oil to be placed in reaction kettle, adds
Enter 150mL water and 0.47g dodecyl trimethyl ammonium bromide, nitrogen purging, stirring rate 300rpm, nitrogen purge simultaneously for stirring
30min is warming up to 210 DEG C of reaction 4h, stops heating, and natural cooling stands liquid separation, and upper layer is dimerization acid product.It is surveyed through GPC
Fixed, dimerization acid content is 45.21% in product, and wherein mononuclear type dimerization acid content is 76%.The glycerol crude product that lower layer distills
In, through detecting, glycerol content 93.21%.
Embodiment 6
It takes commodity tung oil 50mL same as Example 5 to be placed in reaction kettle, 200mL water and 1.41g dodecyl front three is added
Base ammonium bromide, nitrogen purging, stirring rate 400rpm, nitrogen purge 20min, are warming up to 200 DEG C of reaction 5h simultaneously for stirring, stop
Heating, natural cooling stand liquid separation, and upper layer is dimerization acid product.It being measured through GPC, dimerization acid content is 43.17% in product,
Middle mononuclear type dimerization acid content is 72%.
Embodiment 7
It takes commodity tung oil 50mL same as Example 5 to be placed in reaction kettle, 50mL water and 0.235g dodecyl front three is added
Base ammonium bromide, nitrogen purging, stirring rate 400rpm, nitrogen purge 30min, are warming up to 180 DEG C of reaction 6h simultaneously for stirring, stop
Heating, natural cooling stand liquid separation, and upper layer is dimerization acid product.It being measured through GPC, dimerization acid content is 42.02% in product,
Middle mononuclear type dimerization acid content is 73%.
Embodiment 8
It takes commodity tung oil 50mL same as Example 5 to be placed in reaction kettle, 300mL water and 2.35g dodecyl front three is added
Base ammonium bromide, nitrogen purging, stirring rate 500rpm, nitrogen purge 30min, are warming up to 220 DEG C of reaction 3h simultaneously for stirring, stop
Heating, natural cooling stand liquid separation, and upper layer is dimerization acid product.It being measured through GPC, dimerization acid content is 44.85% in product,
Middle mononuclear type dimerization acid content is greater than 70%.
Comparative example 1
With embodiment 1, difference is for eleostearic acid to be changed to cotton oil acid, tall oil acid, soybean oil for preparation process and operating condition
Dimerization acid product is made in any one in acid, corn oleic acid, oleic acid, linoleic acid, stearic acid.It is measured through GPC, dimerization in product
Acid content is lower than 1%.
Comparative example 2
With embodiment 1, difference is for tung oil to be changed to cottonseed oil tall oil, soybean oil, corn for preparation process and operating condition
Dimerization acid product is made in any one in oil, sunflower oil.It is measured through GPC, dimerization acid content is lower than 1% in product.
Claims (12)
1. a kind of dimeric dibasic acid, it is characterised in that: the molecular formula of dimeric dibasic acid is C34H58(COOH)2, wherein mononuclear type dimerization acid content
Greater than 70%.
2. the preparation method of dimeric dibasic acid described in claim 1, it is characterised in that: using eleostearic acid as raw material, nitrogen is blown simultaneously for stirring
It sweeps, is warming up to 180-230 DEG C of reaction, obtains dimerization acid product after the reaction was completed.
3. according to the method described in claim 2, it is characterized by: the eleostearic acid can use commodity eleostearic acid or self-control
Eleostearic acid.
4. according to the method described in claim 2, it is characterized by: the speed of agitator is 50-500rpm, preferably 200-
400rpm；The nitrogen purge time is 1-30min, preferably 20-30min；The reaction temperature is 180-230 DEG C, preferably
200-220℃；Reaction time is 2-7h, preferably 3-5h.
5. according to the method described in claim 2, being cooled to room temperature it is characterized by: cooled down after the reaction was completed.
6. the preparation method of dimeric dibasic acid described in claim 1, it is characterised in that: using tung oil as raw material, exist in catalyst, water
Under, nitrogen purges simultaneously for stirring, is warming up to 170-220 DEG C of reaction, obtains dimerization acid product after the reaction was completed.
7. according to the method described in claim 6, it is characterized by: in the tung oil be mainly eleostearic acid glyceryl ester, adopt
With commodity tung oil or self-control tung oil.
8. according to the method described in claim 6, it is characterized by: the catalyst is quaternary ammonium salt catalyst, additive amount
It is the 5 ‰ -5% of tung oil quality；The additive amount of the water is the volume ratio 1:1-6:1 for making water and tung oil.
9. the method according to claim 6 or 8, it is characterised in that: the catalyst is tetrabutylammonium bromide, the tetrabutyl
Ammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium bromide, trimethyl chlorine
Change one or more of ammonium, tetradecyl trimethyl ammonium chloride, additive amount is the 1%-3% of tung oil quality；The addition of the water
Amount is the volume ratio 3:1-4:1 for making water and tung oil.
10. according to the method described in claim 6, it is characterized by: the speed of agitator is 50-500rpm, preferably
200-400rpm；Nitrogen purge time is 1-30min, preferably 20-30min；Answering temperature is 170-220 DEG C, preferably 200-210
℃；Reaction time is 2-7h, preferably 3-5h.
11., will be cold according to the method described in claim 6, be cooled to room temperature it is characterized by: cooled down after the reaction was completed
But product carries out settle and separate after, and supernatant liquid is dimerization acid product, then water is distilled off in lower liquid and obtains glycerol production.
12. the application of dimeric dibasic acid described in claim 1, it is characterised in that: be used to prepare polyamide, hot melt adhesive, lubricating oil.
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