CN106391114A - Immobilized ionic liquid catalyst and application thereof - Google Patents
Immobilized ionic liquid catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to an immobilized ionic liquid catalyst and application thereof. The immobilized ionic liquid catalyst has a general structural formula as defined in the specification. In the general structural formula, P is a nanometer macroporous resin matrix; n is an integer in a range of 2 to 12; and M<-> is a negative ion selected from a group consisting of a trifluoromethanesulfonate group, a p-toluenesulfonate group, a benzenesulfonate group, a methanesulfonate group, a tetrafluoroborate group and a hexafluorophosphate group. The immobilized ionic liquid catalyst can be applied to industrial olefine acid addition for preparation of corresponding esters.
Description
Technical field
The present invention relates to a kind of supported ionic-liquid catalyst and application thereof.
Background technology
Butyl acrylate is a kind of important high polymer monomer and organic intermediate, at normal temperatures for colourless
Transparency liquid, has weatherability, the chemical and physical properties that water-fast, oil resistant, chemicals-resistant etc. are good.
The industrial method producing acrylate mainly has nitrile Ethanol Method, acrylonitrile hydrolysis method, acroleic acid esterification
Method and ester-interchange method.External BASF, ROHM AND HAAS, Rhizoma Sparganii, Japan go out light petrochemistry strain formula
Commercial firm, Ai Lefu atropic chemistry etc. all carry out scientific research and development to it, are concentrated mainly on changing of production technology
Enter, including multiphase azeotropic technique.The exploitation of new catalyst system and catalyzing, including heteropoly acid and its esters, solid
Super acids, large pore zeolite system, ion exchange resin system.
Alkene and low-carbon (LC) carboxylic acid can prepare ester under the catalyzing cation exchange resin containing sulfonic acid group,
Document US3678099, US2678332, US3031495, US3172905 and US3173943 are
Have been reported that.One defect of the method is the olefinic polymerization phenomenon occurring in esterification process, this polymerization
Lead to yield to decline, and form as follow-up product in the by-product impact of dimer separate, such as isobutene.
Dimer forms azeotropic mixture with butyl acetate, and product separates difficult.
Document US3644497 describes and a kind of contains unsaturated bond using improved catalyst
Alkene and carboxylic acid reaction, the catalyst of employing is molybdenum or tungsten lamp heteropolyacid catalyst.Urge under anhydrous condition
Change preferably 20～140 DEG C of the temperature of reaction, pressure is preferably 0～3000PSIG；And having water condition
Under temperature, pressure then slightly harsh, preferably 50～175 DEG C of temperature, pressure is preferably 0～4000PSIG.
According to the difference of required product, the water yield also respective change of reaction system.Flat according to alcohol and corresponding esters
Weighing apparatus, water is 1～75 with the mol ratio of alkene.
Document US5384426 describes one kind using acidic resins as catalyst propylene and acetic acid
The technique that isopropyl acetate is prepared in esterification.Propylene is derived from cracking of oil or iso-butane is dehydrated preparing isobutene
By-product.It is 0.5～1 in olefin(e) acid mol ratio, pressure is 15～50kg/cm2, temperature is 70～120 DEG C
Under reacted, through distillation after, the purity of isobutyl acetate is up to 99.9%.
Document US6849759B1 describes a kind of method producing organic ester, predominantly miscellaneous in load
The lower technical process producing ethyl acetate of the catalysis of polyacid or salt.
In recent years, ionic liquid is explored eco-friendly catalyst system and catalyzing for people and is provided wide sky
Between, itself there is excellent chemically and thermally mechanical stability, there's almost no vapour pressure at room temperature,
It is made to be applied to during catalytic reaction, have the characteristic being easy to that product separates and catalyst reclaims concurrently.Gu et al.
(J.Mol.Catal.A:Chem., 2004,212:71～75) examined using sulfonic acid funtionalized ionic liquid
Examine its catalysis activity in multiple alkene esterifications.It is found that catalyst is in most of alkene
In can obtain good catalysis activity, simultaneously because the characteristic of ionic liquid itself, after reaction terminates,
Catalyst and product only need to be toppled over and can be separated, and repeating after ionic liquid is vacuum dried again makes
With.Document CN1600773A describes one kind with sulfonic acid funtionalized ionic liquid for catalyst alkene
Hydrocarbon and the method for organic acid synthetic ester, contain sulfonic alkyl pyridine or 1,3- dioxane using end
The ionic liquid that base glyoxaline cation and anion are constituted is catalyst, and 0.1～2.0MPa,
At 50～150 DEG C, catalysis acetic acid is reacted with propylene, and more than 66%, selectivity reaches acetic acid conversion ratio
100%.Although repeated use 4 times after, the catalytic efficiency of catalyst does not reduce.But, institute
Just can need to be continuing with after being vacuum dried after extraction with ionic-liquid catalyst.
As can be seen here, a kind of high activity, high selectivity and segregative olefin(e) acid addition catalysis are researched and developed
System seems particularly significant.
Content of the invention
One of the object of the invention aims to provide a kind of new supported ionic-liquid catalyst.The present invention
The two of purpose aim to provide a kind of purposes of described supported ionic-liquid catalyst.This is supported
Ionic-liquid catalyst is used for during olefin(e) acid addition thering is catalysis activity height, not easy in inactivation, and product is easy
Detached feature.
One of for achieving the above object, the technical solution used in the present invention is as follows：A kind of immobilized
Ionic-liquid catalyst, there is following general structure：
Wherein,For nanometer macroporous resin matrix；N is 2 to 12 integer；M-For anion,
Selected from trifluoromethanesulfonic acid root, p-methyl benzenesulfonic acid root, benzenesulfonic acid root, Loprazolam root, four fluoro boric acid
Root or hexafluoro close phosphate radical.
It is preferable that n is 2 to 4 integer in technique scheme.
It is preferable that M in technique scheme-For trifluoromethanesulfonic acid root.
In technique scheme it is preferable that described nanometer macroporous resin matrix be styrene monomer,
The nanometer macroporous type copolymer that comonomer, nano material obtain through in-situ copolymerization.Wherein, described benzene
Vinyl monomer is selected from least one in styrene, α-methyl styrene or 4- butylstyrene.
Described comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenyl first
At least one in alkane or divinylbenzene.Described nano material is selected from multi-walled carbon nano-tubes, single wall carbon
At least one in nanotube, C60 or C70 fullerene.Described porogen is selected from aliphatic hydrocarbon, polyphenyl
At least one in ethylene, gasoline, fatty acid or paraffin.
Two for achieving the above object, the technical solution used in the present invention is as follows：Described immobilized
Ionic-liquid catalyst be used for the esterification of catalyzed alkene and organic acid.
It is preferable that described esterification condition is in technique scheme：Supported ionic liquid
The weight of catalyst and reactant mixture is than for 0.001～0.1；Alkene is 1 with the mol ratio of organic acid：
5～5：1；Reaction temperature is 60～150 DEG C, and reaction pressure is 0.5～3.0 MPa.
It is preferable that described alkene is C for carbon chain lengths in technique scheme2To C18Straight chain,
Side chain or cyclic olefin.
It is preferable that described organic acid is C in technique scheme1To C18Aliphatic or aromatic acid.
The preparation method of supported ionic-liquid catalyst of the present invention, comprises the following steps：
A) auxiliary agent is made into the water solution A that weight percent concentration is 0.5～2%, by phenylethylene
Monomer, comonomer, nano material, initiator and porogen wiring solution-forming B；Wherein,
Described styrene monomer is selected from styrene, α-methyl styrene or 4- butylstyrene
At least one；
Described comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinylbenzene
At least one in methylmethane or divinylbenzene；
Described nano material is selected from multi-walled carbon nano-tubes, SWCN, C60 or C70 fullerene
In at least one；
Described initiator is selected from benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide or isopropyl
At least one in benzene hydrogen peroxide；
Described auxiliary agent is selected from polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or Calcium Carbonate
In at least one；
Described porogen is selected from least in aliphatic hydrocarbon, polystyrene, gasoline, fatty acid or paraffin
Kind；
In terms of parts by weight, the consumption of styrene monomer is 85～95 parts, and the consumption of comonomer is
2～5 parts, the consumption of nano material is 0.1～3 part, and the consumption of initiator is 0.1～10 part；Help
The consumption of agent is the 150～400% of monomer consumption, the consumption of porogen be monomer consumption 50～
100%；
B) by solution B in 60～75 DEG C of prepolymerizations 0.5～2.5 hour, then by solution B and solution
A mix, be warming up to 70～90 DEG C react 5～15 hours, then be warming up to 90～100 DEG C reaction 5～
15 hours；After reaction terminates, through extracting, washing, filter, be dried, sieve, obtaining particle diameter model
Enclose 0.35～0.60 millimeter of compound macroporous microsphere；
C) make described compound macroporous microsphere chloromethylation：Compound macroporous microsphere adds and is equivalent to again
Close the chloromethylation reagents of macroporous microsphere weight 200～500%, and be equivalent to compound macroporous microsphere weight
The zinc chloride catalyst of amount 20～70%, reacts 8～30 hours at 30～60 DEG C, through filtering,
Washing obtains compound macropore chlorine ball；Described chloromethylation reagents are selected from chloromethyl ether, dichloroethyl ether or Isosorbide-5-Nitrae-two
At least one in chlorine methyl butyl ether；
D) by the mixture of described compound macropore chlorine ball, imidazoles and acetonitrile, react at 60～90 DEG C,
Obtain compound imidazoles microsphere；In described mixture, the mol ratio of compound macropore chlorine ball, imidazoles and acetonitrile
For 1:(1～2):(30～150)；
E) described compound imidazoles microsphere is mixed with sultoness reagent equimolar, room temperature reaction 24～
72 hours, obtain compound glyoxaline cation microsphere；Described sultoness reagent is selected from 1,4- fourth sulfonic acid
Ester, 2,4- butyl sulfonic acid lactones, at least one in PS；
F) described compound glyoxaline cation microsphere and organic sulfonic acid mixing, at 25～60 DEG C reaction 1～
5 hours, obtain described supported ionic-liquid catalyst；Wherein, compound glyoxaline cation microsphere with
The mol ratio of organic sulfonic acid is (1:1)～(1:2)；Described organic sulfonic acid is selected from trifluoromethanesulfonic acid, to toluene
At least one in sulfonic acid, benzenesulfonic acid or Loprazolam.
The ionic-liquid catalyst of the nanometer macroporous resin load of the present invention is used in olefin(e) acid additive reaction,
Catalyst activity is high, and selectivity is high, and product is easily separated, and catalyst can be continuously using multiple.This
Bright preferred version is the in-situ copolymerization of the styrene, divinylbenzene and multi-walled carbon nano-tubes of chloromethylation
Resin matrix and imidazoles react, and form the complex microsphere with imidazole group, then pass through imidazole radicals
Group is reacted with Isosorbide-5-Nitrae-butyl sultone, finally reacts preparation nanometer macroporous resin again with trifluoromethanesulfonic acid and bears
The ionic-liquid catalyst carrying.The ionic-liquid catalyst of this nanometer of macroporous resin load is used for butene-1
In the reaction that sec-butyl acrylate is prepared in methacrylic acid addition, catalyst activity is high, metering system
The conversion ratio of acid may be up to 94.1%, and the selectivity of the secondary butyl ester of methacrylic acid may be up to 100%, and
Product is easily separated, and continuously using 6 times, activity has no and is decreased obviously catalyst, achieves preferable skill
Art effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Add 58.0 grams of styrene in 500 milliliters of there-necked flasks, 1.6 grams of divinylbenzene, 30 grams
Polystyrene and 0.6 gram of benzoyl peroxide initiator, stirring reaction 2.0 hours at 60 DEG C；So
Add 1.6 grams of multi-walled carbon nano-tubes afterwards, continue stirring and carry out prepolymerization in 1 hour.Add and be dissolved with
260 ml deionized water solution of 2.5 grams of polyvinyl alcohol.Adjust mixing speed, progressively heat up simultaneously
To 80 DEG C, react 5 hours；It is warmed up to 90 DEG C again, react 5 hours, be finally warming up to 98 DEG C,
Reaction 6 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes several times, then
Washed with cold water several times, then filter, put into 80 DEG C of drying in baking oven, sieve, collection cut size exists
Compound macroporous microsphere A in the range of 0.35～0.60mm.
Compound macroporous microsphere chloromethylation：In the there-necked flask of 500ml, 50 grams are added to be combined greatly
Hole microsphere A and 250ml chloromethyl ether, room temperature stands 4 hours, starts to stir, adds 15 grams of chlorinations
Zinc is catalyst, is warming up to 50 DEG C and reacts 18 hours, chloromethylation is cooled to room temperature after terminating,
Leach chlorination mother solution, use methanol cyclic washing, dry 8 hours at 100 DEG C, obtain compound big
Hole chlorine ball A.
(chlorinity is 1.5mmol to add 30 grams of compound macropore chlorine ball A in 500ml there-necked flask
Cl/g), imidazoles (45.0mmol) and 220ml acetonitrile, react 16 hours at 80 DEG C, are cooled to
Room temperature, filters, is washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol successively,
Then 60 DEG C of vacuum is dried and is obtained within 12 hours compound imidazoles microsphere A.
In 250ml there-necked flask, add 30 grams of compound imidazoles microsphere A, the Isosorbide-5-Nitrae of equimolar amountss-
Butyl sultone and 200ml acetonitrile, are stirred at room temperature back flow reaction 48 hours, reaction terminates
Afterwards, pour out supernatant liquid, wash microsphere with toluene for several times, be then vacuum dried standby, answered
Close glyoxaline cation microsphere A.
In 250ml there-necked flask, add 30 grams of compound glyoxaline cation microsphere A, equimolar amountss
Trifluoromethanesulfonic acid and acetonitrile, at 40 DEG C react 2 hours, reaction terminate after, pour out upper strata
Liquid, washs microsphere for several times with toluene, ether, the nanometer obtaining the present invention after vacuum drying is big respectively
The resin-carried ionic-liquid catalyst in hole, is designated as Cat-A, and its structural formula is
【Embodiment 2】
(the 60.0 grams of benzene of the monomer mixture solution containing initiator are added in 500 milliliters of there-necked flasks
Ethylene, 2.5 grams of divinylbenzene, 60 grams of polystyrene, 0.6 gram of multi-walled carbon nano-tubes and 1.0 grams of mistakes
BP, this solution was prior to 70 DEG C of stirring reactions 0.5 hour), start agitator, add 200
Ml deionized water and the mixed solution of 5 grams of gelatin, are warming up to 85 DEG C, react 3 hours, then rise
Temperature, to 90 DEG C, is reacted 9 hours, is finally warming up to 100 DEG C, reacts 10 hours.After reaction terminates,
Pour out supernatant liquid, with 85 DEG C of hot washes, then washed with cold water, then filter, put into baking
In case, 80 DEG C of drying, sieve, compound macropore in the range of 0.35～0.60 millimeter for the collection cut size is micro-
Ball B.
The chloromethylation of complex microsphere：In 500 milliliters of there-necked flask, 50 grams of addition is compound micro-
Ball B and 200 milliliters of dichloroethyl ethers, room temperature stands 6 hours, starts to stir, adds 30 grams of zinc chloride
For catalyst, it is warming up to 50 DEG C and reacts 30 hours, chloromethylation is cooled to room temperature after terminating, and leaches
Chlorination mother solution, uses methanol cyclic washing, dries 8 hours at 100 DEG C, obtains compound macropore chlorine ball
B.
(chlorinity is 1.2mmol to add 50 grams of compound macropore chlorine ball B in 500ml there-necked flask
Cl/g), imidazoles (60.0mmol) and 260ml acetonitrile, react 16 hours at 80 DEG C, are cooled to
Room temperature, filters, is washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol successively,
Then 60 DEG C of vacuum is dried and is obtained within 12 hours compound imidazoles microsphere B.
In 250ml there-necked flask, 30 grams of compound imidazoles microsphere B of addition, the 1,3- of equimolar amountss
Propane sultone and 200ml acetonitrile, are stirred at room temperature back flow reaction 48 hours, reaction terminates
Afterwards, pour out supernatant liquid, wash microsphere with toluene for several times, be then vacuum dried standby, answered
Close glyoxaline cation microsphere B.
In 250ml there-necked flask, add 30 grams of compound glyoxaline cation microsphere B, equimolar amountss
Trifluoromethanesulfonic acid and acetonitrile, at 40 DEG C react 2 hours, reaction terminate after, pour out upper strata
Liquid, washs microsphere for several times with toluene, ether, the nanometer obtaining the present invention after vacuum drying is big respectively
The resin-carried ionic-liquid catalyst in hole, is designated as Cat-B, and its structural formula is
【Embodiment 3】
Change【Embodiment 1】In anion (adopt p-methyl benzenesulfonic acid, consumption is and be combined imidazoles
Cationic microspheres A equimolar), remaining preparation condition with【Embodiment 1】Identical, finally obtain Cat-C,
Its structural formula is
【Embodiment 4】
Change【Embodiment 2】In anion (adopt p-methyl benzenesulfonic acid, consumption is and be combined imidazoles
Cationic microspheres B equimolar), remaining preparation condition with【Embodiment 1】Identical, finally obtain Cat-D,
Its structural formula is
【Embodiment 5】
The ionic-liquid catalyst of the nanometer macroporous resin load of above-mentioned preparation is used for C4 and methyl-prop
The reaction of olefin(e) acid, condition is as follows：In autoclave, add 43.0 grams of methacrylic acids, 5.0
The ionic-liquid catalyst Cat-A of gram nanometer macroporous resin load, is filled with 140.0 grams of 1-butylene, fills
Enter High Purity Nitrogen, maintenance reaction pressure is 1.5MPa, reaction temperature is 80 DEG C, mistake after reacting 3 hours
Filter catalyst, recording methacrylic acid conversion ratio is 94.1%, the choosing of the secondary butyl ester of methacrylic acid
Selecting property is 100%.
【Embodiment 6-8】
Change【Embodiment 5】In the catalyst being adopted, with catalyst Cat-B, Cat-C and
Cat-D replaces Cat-A, the olefin(e) acid addition esterification of catalysis methacrylic acid and 1-butylene.Remove and urge
Outside agent changes, other reactions steps and condition and【Embodiment 5】Identical, reaction terminates laggard
Row analysis test, test result see table.
| Embodiment | Catalyst | Conversion ratio % | Selectivity % |
| 6 | Cat-B | 93.8 | 100 |
| 7 | Cat-C | 92.0 | 100 |
| 8 | Cat-D | 90.6 | 100 |
【Embodiment 9-13】
【Embodiment 5】In catalyst Cat-A after the completion of reaction, and reactants separate, toluene,
Ether washs for several times, is then vacuum dried.Then according to【Embodiment 5】In reactions steps and anti-
Answer condition, the olefin(e) acid addition esterification of catalysis methacrylic acid and 1-butylene, obtain catalyst Cat-A
Recycle the result of 2 times, see table.By that analogy, being circulated number of times respectively is 3-6 time
Catalytic reaction, reaction result see table.
| Embodiment | Cycle-index | Conversion ratio % | Selectivity % |
| 9 | 2 | 93.7 | 100 |
| 10 | 3 | 94.0 | 100 |
| 11 | 4 | 93.8 | 100 |
| 12 | 5 | 93.5 | 100 |
| 13 | 6 | 93.9 | 100 |
【Embodiment 14】
In autoclave, add 60.0 grams of acetic acid, 15.0 grams of nanometer macroporous resin loads from
Sub- liquid catalyst Cat-A, is filled with 126.0 grams of propylene, is filled with High Purity Nitrogen, and maintenance reaction pressure is
1.5MPa, reaction temperature is 120 DEG C, Filtration of catalyst after reacting 3 hours, records acetic acid and turns
Rate is 94.3%, and the selectivity of isopropyl acetate is 100%.
【Comparative example 1】
【Comparative example 1】As【Embodiment 14】Comparative example.Catalyst adopts trifluoromethanesulfonic acid
1- hexyl -3- (4- sulfonic group) 1-Butyl-1H-imidazole ionic liquid (preparation method is shown in document CN1600773A),
Consumption is 21.5 grams, adds the catalyst of above-mentioned consumption in autoclave, 4.5 grams of acetic acid, 9.45
Gram propylene, is filled with High Purity Nitrogen, and maintenance reaction pressure is 3.0MPa, and reaction temperature is 120 DEG C, reaction
Sample analysis after 4 hours, recording acetic acid conversion ratio is 85.5%, and the selectivity of isopropyl acetate is
100%.
【Embodiment 16】
By the ionic-liquid catalyst Cat-A of the nanometer macroporous resin of preparation load be used for different alkene with
The esterification additive reaction of organic acid, condition is as follows：In autoclave, sequentially add catalyst,
Alkene, carboxylic acid, wherein catalyst account for the 1.5% of reactant mixture quality；Alkene and carboxylic acid mole
Than for 3：1, it is subsequently charged with High Purity Nitrogen, maintain reaction system to be in liquid-phase condition, anti-at 120 DEG C
Answer 4 hours, be subsequently cooled to room temperature, sample analysis.Response analysises result is as shown in the table.
| Alkene | Carboxylic acid | Conversion ratio % | Selectivity % |
| 2- methyl-2-butene | Acetic acid | 98.7 | 100 |
| 1- octene | Acetic acid | 95.8 | 100a |
| Cyclopentenes | Acetic acid | 93.5 | 100 |
| Bicyclopentadiene | Acetic acid | 94.0 | 100 |
| Propylene | Acetic acid | 82.6 | 100 |
| Propylene | Propanoic acid | 91.6 | 100 |
| Propylene | Acrylic acid | 91.8 | 100 |
| Propylene | Isooctyl acid | 85.8 | 100 |
| 4- phenyl -1-butylene | Phenylacetic acid | 93.0 | 100 |
Note a：Product has three kinds of isomerss, and its ratio is 5：4：1.
b：Reaction temperature is 50 degree, and the response time is 20 hours, and olefin(e) acid mol ratio is 4：1, reaction system
Using toluene as solvent.
Claims (10)
1. a kind of supported ionic-liquid catalyst, has following general structure：
Wherein,For nanometer macroporous resin matrix；N is 2 to 12 integer；M-For anion,
Selected from trifluoromethanesulfonic acid root, p-methyl benzenesulfonic acid root, benzenesulfonic acid root, Loprazolam root, four fluoro boric acid
Root or hexafluoro close phosphate radical.
2. according to claim 1 supported ionic-liquid catalyst it is characterised in that n is
2 to 4 integer；M-For trifluoromethanesulfonic acid root.
3. according to claim 1 supported ionic-liquid catalyst it is characterised in that described
Nanometer macroporous resin matrix is styrene monomer, comonomer, nano material and porogen through in situ
The nanometer macroporous type copolymer that copolymerization obtains.
4. according to claim 3 supported ionic-liquid catalyst it is characterised in that described
Styrene monomer is selected from least one in styrene, α-methyl styrene or 4- butylstyrene.
5. according to claim 3 supported ionic-liquid catalyst it is characterised in that described
Comonomer be selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or
At least one in divinylbenzene.
6. according to claim 3 supported ionic-liquid catalyst it is characterised in that described
Nano material be selected from multi-walled carbon nano-tubes, SWCN, in C60 or C70 fullerene at least
A kind of.
7. according to claim 3 supported ionic-liquid catalyst it is characterised in that described
Porogen is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, fatty acid or paraffin.
8. supported ionic-liquid catalyst described in claim 1 is used for catalyzed alkene and organic acid
Esterification.
9. the purposes of supported ionic-liquid catalyst according to claim 8, its feature exists
In described esterification condition it is：The weight ratio of supported ionic-liquid catalyst and reactant mixture
For 0.001～0.1；Alkene is (1 with the mol ratio of organic acid:5)～(5:1)；Reaction temperature be 60～
150 DEG C, reaction pressure is 0.5～3.0 MPa.
10. the purposes of supported ionic-liquid catalyst according to claim 8, its feature exists
In described alkene for carbon chain lengths be C2To C18Straight chain, side chain or cyclic olefin；Described organic acid
For C1To C18Aliphatic or aromatic acid.
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| CN109777625A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The synthetic method of biodiesel |
| CN109777629A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The preparation method of biodiesel |
| CN114349890A (en) * | 2022-01-28 | 2022-04-15 | 长兴（广州）光电材料有限公司 | Ultrahigh crosslinked resin and preparation method and application thereof |
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