CN116731033B - Preparation method of epoxy isosorbide plasticizer - Google Patents
Preparation method of epoxy isosorbide plasticizer Download PDFInfo
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- CN116731033B CN116731033B CN202311015289.XA CN202311015289A CN116731033B CN 116731033 B CN116731033 B CN 116731033B CN 202311015289 A CN202311015289 A CN 202311015289A CN 116731033 B CN116731033 B CN 116731033B
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims abstract description 69
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 69
- 239000004593 Epoxy Substances 0.000 title claims abstract description 50
- 239000004014 plasticizer Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- -1 rare earth chloride Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- LBIQRIHYRDEVIR-UHFFFAOYSA-N but-2-enyl(dichloro)silane Chemical compound CC=CC[SiH](Cl)Cl LBIQRIHYRDEVIR-UHFFFAOYSA-N 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 4
- 235000020778 linoleic acid Nutrition 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- 229940078916 carbamide peroxide Drugs 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical group OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 208000012839 conversion disease Diseases 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000008035 bio-based plasticizer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to the technical field of plasticizers, in particular to a preparation method of an epoxy isosorbide plasticizer. The invention adopts isosorbide, organic acid, catalyst, solvent, solid sodium bicarbonate, sulfuric acid, glacial acetic acid, oxidant and the like to prepare the epoxy isosorbide plasticizer; the epoxy isosorbide plasticizer is prepared by the resin-supported rare earth catalyst after being repeatedly used for 5 times, the conversion rate is up to 99.5%, and the epoxy value is 12.6%; the method has the advantages of simple process, mild operation conditions, environment-friendly process and applicability to industrial production.
Description
Technical Field
The invention relates to the technical field of plasticizers, in particular to a preparation method of an epoxy isosorbide plasticizer.
Background
The plasticizer is a functional auxiliary agent in polyvinyl chloride (PVC) materials, and has the functions of improving the flexibility, the plasticity, the processability, the stretchability and the like of the PVC. Phthalate plasticizers have been widely used as PVC plasticizers since the 30 s of the 20 th century. However, phthalate plasticizers are environmentally unfriendly and have reproductive toxicity, which are weak in intermolecular forces with polyvinyl chloride, and are easily transferred from the plastic article to the surrounding environment during use. Therefore, how to reduce or replace the use of phthalate plasticizers is becoming an important issue.
Chinese patent application publication No. CN116425766a discloses an epoxy isosorbide plasticizer and a method for preparing the same. The epoxy isosorbide plasticizer is prepared by esterification reaction of isosorbide and linoleic acid and then epoxidation. Such EGLA-ISB plasticizers successfully avoid the constraint relationship between molecular weight and compatibility, and the overall properties (mechanical properties, thermal stability and migration resistance) of PVC plasticized with EGLA-ISB are superior to those of PVC plasticized with DOTP.
Chinese patent application publication No. CN114014870a discloses a method for preparing isosorbide bio-based plasticizer, and products and applications thereof. The preparation method comprises the following steps: the method comprises the steps of taking isosorbide and monocarboxylic acid as raw materials, carrying out esterification reaction under the action of a catalyst to obtain isosorbide, and then carrying out oxidation reaction by taking isosorbide as the raw material to obtain the epoxy isosorbide. The isosorbide and epoxy isosorbide bio-based plasticizer prepared by the method can be applied to the preparation of PVC composite materials, can replace part of traditional o-benzene plasticizers, and the prepared PVC composite materials have excellent mechanical properties and processability.
Chinese patent application publication No. CN114085231a discloses a bio-based isosorbide plasticizer and a method for preparing the same. The method comprises the following steps: (1) The isosorbide and adipic acid are subjected to esterification reaction under the action of a catalyst; (2) Esterifying and blocking the intermediate product obtained by the reaction and a blocking agent under the action of a catalyst to obtain a target product; (3) And (3) washing, extracting, decompressing, distilling and the like the obtained target product by using a saturated sodium chloride aqueous solution to purify the target product, thereby obtaining the bio-based isosorbide plasticizer. The isosorbide plasticizer prepared by the method has the advantages of biodegradability, environmental friendliness, no biotoxicity and the like, and meanwhile, the production cost is low, the process is simple, and the industrialization is easy.
However, the plasticizer prepared by the prior art generally has the problems of complex process, high investment, low conversion rate and the like.
Disclosure of Invention
The invention provides a preparation method of an epoxy isosorbide plasticizer, which aims to solve the problems of complex preparation process and poor conversion rate of the existing plasticizer.
The specific technical scheme of the invention is as follows.
The preparation process of the isosorbide plasticizer includes the following steps:
a1: weighing 120-140 parts of isosorbide according to parts by weight, adding into a reaction kettle, heating to 65-80 ℃, stirring, continuously adding 270-320 parts of organic acid, 2-5 parts of catalyst and 300-400 parts of solvent, and continuously heating for reaction;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 0.5-3 parts of sulfuric acid into isosorbide, mixing uniformly, continuously adding 150-200 parts of glacial acetic acid and 0.5-3 parts of oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished.
In the invention, the organic acid is isovaleric acid or isooctanoic acid or linoleic acid or isononanoic acid.
In the invention, the solvent is benzene or toluene or xylene or carbon tetrachloride.
The reaction temperature in the step A1 is 90-120 ℃ and the reaction time is 1-3h.
The pressure of the reduced pressure distillation in the step A2 is 120-150Pa, and the temperature is 140-180 ℃.
In the invention, the oxidant is carbamide peroxide or peracetic acid or hydrogen peroxide or benzophenone peroxide.
The reaction temperature in the step A3 is 60-90 ℃ and the reaction time is 5-8h.
In the invention, the catalyst is a resin-supported rare earth catalyst, and the resin-supported rare earth catalyst is obtained by respectively carrying out hydrosilylation reaction on isopropenyl rare earth, 1-propenyl methyldichlorosilane and allyl epoxy polyether and loading the catalyst on styrene macroporous sulfonic acid resin.
Further, the preparation method of the resin supported rare earth catalyst comprises the following steps:
b1: adding 4-10 parts of rare earth chloride and 2-5 parts of anhydrous Na according to parts by mass 2 CO 3 Adding 10-22 parts of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 15-30 parts of isopropenyl rare earth, 25-50 parts of 1-propenyl methyldichlorosilane, 0.5-3.6 parts of allyl epoxy polyether and 2500-3000 parts of toluene are added into a reaction kettle, high-purity nitrogen is used for protection, 0.1-2 parts of chloroplatinic acid isopropanol solution is dripped into the reaction kettle, the temperature is controlled at 60-70 ℃, stirring is carried out for 2-5h, 300-500 parts of dry styrene type large Kong Huangsuan resin, 1-4 parts of benzoyl peroxide and 60-70 ℃ are added, stirring is carried out for 10-20h, filtering and drying are carried out, and the resin supported rare earth catalyst is obtained.
And in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 2-8%.
Compared with the prior art, the invention has the following advantages:
1. the method for preparing the epoxy isosorbide plasticizer by using the resin-supported rare earth catalyst after being repeatedly used for 5 times has the conversion rate up to 99.5 percent and the epoxy value of 12.6 percent, and is obviously improved compared with the prior art.
2. The method has the advantages of simple process, mild operation conditions, environment-friendly process and applicability to industrial production.
3. The invention uses the resin to load the rare earth catalyst, the catalyst can be simply separated, the catalyst can not be immersed into the product, the catalytic active components are not easy to run off, and the catalyst can be used for a long time.
Detailed Description
The epoxy value of the epoxy isosorbide plasticizer prepared by the invention is measured according to the reference standard GB/T1677-2008, and the detection data is the conversion rate and the epoxy value of the resin-supported rare earth catalyst after being repeatedly used for 5 times.
Example 1: the preparation process of the isosorbide plasticizer includes the following steps:
a1: 120g of isosorbide is weighed and added into a reaction kettle, the reaction kettle is heated to 65 ℃, 270g of organic acid, 2g of catalyst and 300g of solvent are continuously added into the reaction kettle under stirring, and the temperature is continuously increased for reaction;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 0.5g sulfuric acid into isosorbide, mixing uniformly, then continuously adding 150g glacial acetic acid and 0.5g oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished.
The organic acid is isovaleric acid.
The solvent is benzene.
The reaction temperature in the step A1 is 90 ℃ and the reaction time is 1h.
The reduced pressure distillation pressure in the step A2 is 120Pa, and the temperature is 140 ℃.
The oxidant is carbamide peroxide.
The reaction temperature in the step A3 is 60 ℃ and the reaction time is 5h.
The catalyst is a resin-supported rare earth catalyst, and the preparation method comprises the following steps:
b1: adding 4g of rare earth chloride and 2g of anhydrous Na 2 CO 3 Adding 10g of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 15g of isopropenyl rare earth, 25g of 1-propenyl methyl dichlorosilane, 0.5g of allyl epoxy polyether and 2500g of toluene are added into a reaction kettle, high-purity nitrogen is used for protection, 0.1g of chloroplatinic acid isopropyl alcohol solution is dripped into the reaction kettle, the temperature is controlled at 60 ℃, stirring is carried out for 2 hours, 300g of dry D006 styrene series large Kong Huangsuan resin, 1g of benzoyl peroxide is added, stirring is carried out at 60 ℃ for 10 hours, filtering and drying are carried out, and the resin supported rare earth catalyst is obtained.
And in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 2%.
The epoxy value of the epoxy isosorbide plasticizer in the example is 10.9% and the reaction conversion is 98.3% by test analysis.
Example 2: the preparation process of the isosorbide plasticizer includes the following steps:
a1: weighing 125g of isosorbide, adding the isosorbide into a reaction kettle, heating to 70 ℃, stirring, continuously adding 290g of organic acid, 3g of catalyst and 340g of solvent, and continuously heating to react;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 1g of sulfuric acid into the isosorbide, uniformly mixing, continuously adding 160g of glacial acetic acid and 1g of oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished.
The organic acid is isooctanoic acid.
The solvent is toluene.
The reaction temperature of the step A1 is 100 ℃ and the time is 1.5h.
The reduced pressure distillation pressure in the step A2 is 130Pa, and the temperature is 150 ℃.
The oxidant is peracetic acid.
The reaction temperature in the step A3 is 70 ℃ and the reaction time is 6h.
The catalyst is a resin-supported rare earth catalyst, and the preparation method comprises the following steps:
b1: adding 6g of rare earth chloride and 3g of anhydrous Na 2 CO 3 Adding 14g of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 20g of isopropenyl rare earth, 30g of 1-propenyl methyl dichlorosilane, 1g of allyl epoxy polyether and 2600g of toluene are added into a reaction kettle, high-purity nitrogen is used for protection, 1g of chloroplatinic acid isopropyl alcohol solution is dripped into the reaction kettle, the temperature is controlled to be 65 ℃, stirring is carried out for 3 hours, 350g of dry D001 styrene series large Kong Huangsuan resin, 2g of benzoyl peroxide and stirring at 65 ℃ are carried out for 14 hours, and then the resin supported rare earth catalyst is obtained after filtering and drying.
And in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 4%.
The epoxy value of the epoxy isosorbide plasticizer in the example is 11.4% and the reaction conversion is 98.9% by test analysis.
Example 3: the preparation process of the isosorbide plasticizer includes the following steps:
a1: weighing 135g of isosorbide, adding into a reaction kettle, heating to 75 ℃, stirring, continuously adding 300g of organic acid, 4g of catalyst and 380g of solvent, and continuously heating to react;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 2g of sulfuric acid into the isosorbide, uniformly mixing, continuously adding 180g of glacial acetic acid and 2g of oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished.
The organic acid is linoleic acid.
The solvent is dimethylbenzene.
The reaction temperature of the step A1 is 110 ℃ and the time is 2.5h.
The reduced pressure distillation pressure in the step A2 is 140Pa, and the temperature is 170 ℃.
The oxidant is hydrogen peroxide.
The reaction temperature in the step A3 is 80 ℃ and the reaction time is 7h.
The catalyst is a resin-supported rare earth catalyst, and the preparation method comprises the following steps:
b1: adding 8g of rare earth chloride and 4g of anhydrous Na 2 CO 3 Adding 19g of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 25g of isopropenyl rare earth, 45g of 1-propenyl methyldichlorosilane, 3g of allyl epoxy polyether and 2800g of toluene are added into a reaction kettle, a high-purity nitrogen protection is used, 1.5g of chloroplatinic acid isopropyl alcohol solution is dripped into the reaction kettle, the temperature is controlled to be 65 ℃, stirring is carried out for 4 hours, 450g of D001 dry-based styrene series large Kong Huangsuan resin, 3g of benzoyl peroxide and stirring at 65 ℃ are carried out for 18 hours, and filtering and drying are carried out, so that the resin supported rare earth catalyst is obtained.
And in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 6%.
The epoxy value of the epoxy isosorbide plasticizer in the example is 12.7% and the reaction conversion is 99.6% by test analysis.
Example 4: the preparation process of the isosorbide plasticizer includes the following steps:
a1: weighing 140g of isosorbide, adding the isosorbide into a reaction kettle, heating to 80 ℃, stirring, continuously adding 320g of organic acid, 5g of catalyst and 400g of solvent, and continuously heating to react;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 3g of sulfuric acid into the isosorbide, uniformly mixing, continuously adding 200g of glacial acetic acid and 3g of oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished.
The organic acid is isononanoic acid.
The solvent is carbon tetrachloride.
The reaction temperature of the step A1 is 120 ℃ and the reaction time is 3h.
The reduced pressure distillation pressure in the step A2 is 150Pa, and the temperature is 180 ℃.
The oxidant is benzophenone peroxide.
The reaction temperature in the step A3 is 90 ℃ and the reaction time is 8 hours.
The catalyst is a resin-supported rare earth catalyst, and the preparation method comprises the following steps:
b1: adding 10g of rare earth chloride and 5g of anhydrous Na 2 CO 3 Adding 22g of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 30g of isopropenyl rare earth, 50g of 1-propenyl methyl dichlorosilane, 3.6g of allyl epoxy polyether and 3000g of toluene are added into a reaction kettle, high-purity nitrogen is used for protection, 2g of chloroplatinic acid isopropyl alcohol solution is dripped into the reaction kettle, the temperature is controlled to be 70 ℃, stirring is carried out for 5 hours, 500g of dry D001 styrene series large Kong Huangsuan resin, 4g of benzoyl peroxide is added, stirring is carried out for 20 hours at 70 ℃, filtering and drying are carried out, and the resin supported rare earth catalyst is obtained.
And in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 8%.
The epoxy value of the epoxy isosorbide plasticizer in the example is 12.2% and the reaction conversion is 99.2% by test analysis.
Comparative example 1: the catalyst was p-toluenesulfonic acid, otherwise as in example 1.
The epoxy value of the epoxide isosorbide plasticizer in the comparative example is 5.6% and the reaction conversion is 87.5% through test analysis.
Comparative example 2: the procedure of example 1 was repeated except that isopropenyl rare earth was not added.
The epoxy value of the epoxy isosorbide plasticizer in the comparative example is 7.8% and the reaction conversion is 91.8% through test analysis.
Comparative example 3: 1-propenyl methyldichlorosilane was not added and the procedure of example 1 was followed.
The epoxy value of the epoxide isosorbide plasticizer in the comparative example is 8.3% and the reaction conversion is 93.2% through test analysis.
Compared with the data of the comparative example, the conversion rate of the epoxy isosorbide plasticizer prepared by the resin-supported rare earth catalyst after the repeated use of the invention for 5 times is up to 99.5%, and the epoxy value is 12.6%, which is obviously improved compared with the prior art.
The above examples only represent a few embodiments of the present invention, which are described in more specific detail, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which is intended to be within the scope of the invention as defined in the appended claims.
Claims (6)
1. A method for preparing an epoxy isosorbide plasticizer, comprising the steps of:
a1: weighing 120-140 parts of isosorbide according to parts by weight, adding into a reaction kettle, heating to 65-80 ℃, stirring, continuously adding 270-320 parts of organic acid, 2-5 parts of catalyst and 300-400 parts of solvent, and continuously heating for reaction;
a2: after the reaction is finished, removing the solvent by reduced pressure distillation, adding solid sodium bicarbonate to neutralize the catalyst, removing water by reduced pressure, and collecting fractions by reduced pressure distillation to obtain isosorbide;
a3: adding 0.5-3 parts of sulfuric acid into isosorbide, uniformly mixing, continuously adding 150-200 parts of glacial acetic acid and 0.5-3 parts of oxidant, stirring, heating, and obtaining the epoxy isosorbide plasticizer after the reaction is finished;
the catalyst is a resin-supported rare earth catalyst, and the preparation method comprises the following steps:
b1: adding 4-10 parts of rare earth chloride and 2-5 parts of anhydrous Na according to parts by mass 2 CO 3 Adding 10-22 parts of isopropenyl acetate, heating until no bubbles are generated, cooling, and removing the solvent by suction filtration to obtain isopropenyl rare earth;
b2: 15-30 parts of isopropenyl rare earth, 25-50 parts of 1-propenyl methyldichlorosilane, 0.5-3.6 parts of allyl epoxy polyether, 2500-3000 parts of toluene are added into a reaction kettle, high-purity nitrogen is used for protection, 0.1-2 parts of chloroplatinic acid isopropanol solution is dripped into the reaction kettle, the temperature is controlled at 60-70 ℃, stirring is carried out for 2-5 hours, 300-500 parts of dry styrene type large Kong Huangsuan resin, 1-4 parts of benzoyl peroxide and 60-70 ℃ are added, stirring is carried out for 10-20 hours, filtering and drying are carried out, and the resin-supported rare earth catalyst is obtained;
the organic acid is isovaleric acid or isooctanoic acid or linoleic acid or isononanoic acid;
the oxidant is carbamide peroxide or peracetic acid or hydrogen peroxide or benzophenone peroxide.
2. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that: the solvent is benzene or toluene or xylene or carbon tetrachloride.
3. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that: the reaction temperature of the step A1 is 90-120 ℃ and the reaction time is 1-3h.
4. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that: the reduced pressure distillation pressure in the step A2 is 120-150Pa, and the temperature is 140-180 ℃.
5. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that: the reaction temperature of the step A3 is 60-90 ℃ and the reaction time is 5-8h.
6. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that: and in the step B2, the mass percentage concentration of the chloroplatinic acid isopropanol solution is 2-8%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724154A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Isosorbide ester plasticizer and preparation method thereof |
| CN114014870A (en) * | 2021-11-23 | 2022-02-08 | 北京工商大学 | Preparation method of isosorbide ester bio-based plasticizer, product and application thereof |
| CN114539619A (en) * | 2022-03-03 | 2022-05-27 | 昕亮科技（深圳）有限公司 | Preparation method of bio-based environment-friendly plasticizer for polyethylene resin |
| CN114591537A (en) * | 2022-04-07 | 2022-06-07 | 昕亮科技（深圳）有限公司 | Bio-based solvent-resistant plasticizer and preparation method thereof |
| CN114751816A (en) * | 2022-04-21 | 2022-07-15 | 盘锦洪鼎化工有限公司 | Method for preparing isooctanoic acid by titanium-silicon molecular sieve supported catalysis |
| CN116425766A (en) * | 2023-04-18 | 2023-07-14 | 北京工商大学 | Epoxy isosorbide plasticizer and preparation method thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724154A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Isosorbide ester plasticizer and preparation method thereof |
| CN114014870A (en) * | 2021-11-23 | 2022-02-08 | 北京工商大学 | Preparation method of isosorbide ester bio-based plasticizer, product and application thereof |
| CN114539619A (en) * | 2022-03-03 | 2022-05-27 | 昕亮科技（深圳）有限公司 | Preparation method of bio-based environment-friendly plasticizer for polyethylene resin |
| CN114591537A (en) * | 2022-04-07 | 2022-06-07 | 昕亮科技（深圳）有限公司 | Bio-based solvent-resistant plasticizer and preparation method thereof |
| CN114751816A (en) * | 2022-04-21 | 2022-07-15 | 盘锦洪鼎化工有限公司 | Method for preparing isooctanoic acid by titanium-silicon molecular sieve supported catalysis |
| CN116425766A (en) * | 2023-04-18 | 2023-07-14 | 北京工商大学 | Epoxy isosorbide plasticizer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 生物基异山梨醇型环氧固化剂的制备及性能研究;张朝群 等;现代化工;第42卷(第04期);第202-205和211页 * |
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