CN104710388A - Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof - Google Patents
Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof Download PDFInfo
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- CN104710388A CN104710388A CN201510094649.9A CN201510094649A CN104710388A CN 104710388 A CN104710388 A CN 104710388A CN 201510094649 A CN201510094649 A CN 201510094649A CN 104710388 A CN104710388 A CN 104710388A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
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- 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
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Abstract
The invention discloses an epoxy cardanol-based glycidyl ether plasticizer as well as a preparation method and application thereof. The preparation method comprises the following steps: taking cardanol and epoxy chloropropane as main raw materials and carrying out ring-opening addition reaction and ring-closure reaction to synthesize an intermediate product cardanol-based glycidyl ether; and further uniformly mixing the intermediate product with organic acid and a catalyst, heating to a certain temperature, dripping a peroxide source to carry out epoxidation reaction to obtain a crude product, leaving the crude product to stand, layering, performing neutralization and dehydration on the crude product after the reaction so as to obtain an epoxy cardanol-based glycidyl ether plasticizer. The plasticizer is non-toxic, has relatively high plasticizing efficiency and can endowing resin products with favorable thermal stability and mechanical property; and moreover, by taking the cardanol which is low in cost and easy to get as raw material, the epoxy cardanol-based glycidyl ether plasticizer integrates the advantages of being environment-friendly and being reproducible, complies with the developing trend of the plastic additive industry and has wide application and favorable application prospect.
Description
Technical field
The invention belongs to epoxy plasticiser preparing technical field, be specifically related to a kind of method taking cardanol as raw material and prepare epoxy cashew nut phenolic group glycidyl ether softening agent.
Background technology
Softening agent be macromolecular material particularly PVC plastic processing in most important additive, its output accounts for more than 60% of additives for plastics ultimate production.China is that softening agent consumes big country, and current annual production is more than 3,000,000 tons, and wherein phthalic ester plasticizer accounts for more than 80% of total quantity consumed.But there are some researches show, such softening agent has potential genotoxicity and environmental threat, multinational having forbidded strictly of the U.S., Japan and European Union uses in the industries such as electronics, food, daily necessities and toy.At present, research and development and the promotion efficiency of non-toxic plasticizer product has been accelerated abroad.Utilize environmental protection, nontoxic, reproducible softening agent products substitution conventional petroleum base phthalic ester plasticizer, become the important development trend of softening agent industry.
In recent years, the domestic research dynamics increasing environment-friendlyplasticizer plasticizer, but mainly concentrate on the improvement aspect of main flow environment-friendly plasticizer preparation technology, as Ye etc. has synthesized mesopore molecular sieve HMS and doped Ti-HMS, Mn-HMS exploitation Vegetable oil lipoprotein epoxidation novel process; Xu etc. study the application of acidic ion liquid in synthesizing citric acid tri-n-butyl; The Chen Denglong of Fujian Normal University etc. have invented the ionic liquid-catalyzed method (patent publication No. CN101284821A) preparing epoxy aliphatic acid methyl ester, reduce the corrosion of catalyzer to equipment.The development of current Environmental Protection in China softening agent obviously lags behind the needs of functional plastics goods and national life, and exploitation has the environmental protection of independent intellectual property right, the novel green softening agent that inexpensive, builder activity is good is extremely urgent.
Cardanol be extract from forest and agricultural biomass cashew nut shell containing the natural phenolic compound of unsaturated Long carbon chain hydrocarbon, be one of the most frequently used renewable resources, there is renewable, cheap and resourceful unique advantage.At present, the fields such as coating, tamanori, friction materials, pluronic polymer and other biological based high molecular material are mainly used in modified by cardanol derivative.But prepared the method for epoxy cashew nut phenolic group glycidyl ether softening agent by cardanol, there is no report at home and abroad.
Summary of the invention
Day by day limited for phthalic ester plasticizer use range, single and the problems such as ubiquity poor compatibility of conventional epoxy softening agent kind, the invention provides a kind of epoxy cashew nut phenolic group glycidyl ether and its preparation method and application, have that by product is few, constant product quality, technique be simple, the advantage such as low-carbon emission reduction; Prepared softening agent product consistency is good, and plasticizing efficiency is high, and can give mechanical property and the thermostability of resin excellence.
Technical scheme of the present invention is as follows: a kind of epoxy cashew nut phenolic group glycidyl ether, and raw material consists of by weight: 10 ~ 20 parts of cashew nut phenolic group glycidyl ethers, 0.5 ~ 1.5 part of organic acid, account for cardanol quality 2 ~ 3% catalyzer and 3 ~ 10 parts of peroxygen sources; Preparation method obtains cashew nut phenolic group glycidyl ether for adding highly basic ring-closure reaction again after opening by cardanol and epoxy chloropropane under opening catalyzer exists, then cashew nut phenolic group glycidyl ether again with organic acid and catalyst mix evenly and heats up afterwards that dripping peroxygen source carries out epoxidation reaction, after reaction terminates, crude product stratification, neutralization and processed, obtain finished product.
In described cashew nut phenolic group glycidyl ether preparation, the mass ratio of cardanol and epoxy chloropropane is 5 ~ 10:10 ~ 20, and described open loop addition catalyst accounts for 1 ~ 2% of cardanol quality.
Described open loop addition catalyst is one or more mixtures of benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride.
Described highly basic is solid sodium hydroxide or solid potassium hydroxide.
Described organic acid is formic acid or acetic acid.
Described peroxygen source is hydrogen peroxide or tertbutyl peroxide.
The concentration of described hydrogen peroxide is 50% ~ 70%wt.
Described catalyzer is tosic acid.
A preparation method for epoxy cashew nut phenolic group glycidyl ether, is characterized in that,
(1) cashew nut phenolic group glycidyl ether is prepared: by cardanol, epoxy chloropropane and open loop addition catalyst, at 90 ~ 120 DEG C, carry out opening 2 ~ 4h; Continue to add highly basic and carry out ring-closure reaction 3 ~ 5h in 50 ~ 70 DEG C; Again after filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether;
(2) epoxy cashew nut phenolic group glycidyl ether is prepared: cashew nut phenolic group glycidyl ether, organic acid and catalyzer, 3 ~ 10g peroxygen source is dripped in 50 DEG C, after 60 ~ 70 DEG C of reaction 3 ~ 5h, obtain epoxy cashew nut phenolic group glycidyl ether crude product, through stratification, neutralization and processed, obtain environment-friendly epoxy cashew nut phenolic group glycidyl ether.
Epoxy cashew nut phenolic group glycidyl ether is as PVC softening agent or the application in preparation PVC softening agent.
Beneficial effect:
1. the optimal coupling of the present invention epoxidation modification method of cardanol phenolic group modified and side chain thiazolinyl, simplifies production technique, reduces production cost; Reduce side reaction, improve the stability of product oxirane value and product; Reduce the discharge of wastewater in reaction process, energy efficient, shorten the production cycle, there is economic and social benefit preferably.
2. the present invention adopts cardanol to be raw material, utilize the chemical structure feature of cardanol self, epoxidation modification is carried out to its phenolic hydroxyl group and pendant double bonds simultaneously, design and develop the novel multifunctional softening agent with phthalic ester similar, there is excellent plasticization effect and environmental-protecting performance, and be easy to the plasticizer formula technique and the PVC product processing technique that mate current maturation, be beneficial to the marketization and apply.
3. the softening agent that prepared by the present invention has with resin compatible is good, plasticizing efficiency is high, mechanical property and the advantage such as thermal stability is excellent, reaches the requirement of goods processing and application.
Accompanying drawing explanation
The epoxy cashew nut phenolic group glycidyl ether that Fig. 1 the present invention synthesizes
1h NMR spectrogram.
The epoxy cashew nut phenolic group glycidyl ether that Fig. 2 the present invention synthesizes
13c NMR spectrogram.
Softening agent products substitution part dioctyl phthalate (DOP) prepared by Fig. 3 the present invention is for the Dynamic thermo-mechanical property analysis of spectra of PVC product.As can be seen from Figure 3, significantly can reduce the second-order transition temperature of PVC base, there is the plasticizing efficiency that neighbour dioctyl phthalate is higher.
Softening agent products substitution part dioctyl phthalate (DOP) prepared by Fig. 4 the present invention is for the thermogravimetic analysis (TGA) spectrogram of PVC product.Result shows, epoxy cashew nut phenolic group glycidyl ether softening agent can improve the thermostability of PVC product greatly.
Softening agent products substitution part dioctyl phthalate (DOP) prepared by Fig. 5 the present invention is for the volatility of PVC product, extractable and exudative test result.Can find out, epoxy cashew nut phenolic group glycidyl ether has good consistency and volatility resistance, and has good acid and alkali-resistance and organic solvent-borne.
Embodiment
Following examples further illustrate of the present invention, is not limitation of the present invention.
A preparation method for epoxy cashew nut phenolic group glycidyl ether, step is:
(1) by the cardanol of 50 ~ 100g, 100 ~ 200g epoxy chloropropane and appropriate open loop addition catalyst (accounting for 1 ~ 2% of cardanol quality), at 90 ~ 120 DEG C, opening 2 ~ 4h is carried out; Continue to add 5-15g highly basic and 50 ~ 70 DEG C carry out ring-closure reaction 3 ~ 5h; Again after filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.(2) 10 ~ 20g cashew nut phenolic group glycidyl ether, 0.5 ~ 1.5g organic acid and proper catalyst (accounting for 2 ~ 3% of cardanol quality) is taken, 3 ~ 10g hydrogen peroxide is dripped in 50 DEG C, after 60 ~ 70 DEG C of reaction 3 ~ 5h, obtain epoxy cashew nut phenolic group glycidyl ether crude product, through stratification, neutralization and processed, obtain environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent.
Described opening catalyzer is benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, the one of tetramethyl ammonium chloride or or multiple mixture.
Described ring-closure reaction highly basic is solid sodium hydroxide or solid potassium hydroxide.
Described intermediate product, after underpressure distillation process, recycles excessive epoxy chloropropane.
Described organic acid is formic acid or acetic acid.
Described peroxygen source is hydrogen peroxide or tertbutyl peroxide, adopts the mode dripped to add reaction system.
The concentration of described hydrogen peroxide is 50% ~ 70%.
Epoxy cashew nut phenolic group glycidyl ether crude product uses the sodium hydrogen carbonate solution of 5% mass concentration of 30 ~ 60 DEG C respectively, and the deionized water of 40 ~ 70 DEG C or distilled water carry out neutralization &washing, improves product yield, shortens the operating time.
The main physicochemical property of described epoxy cashew nut phenolic group glycidyl ether softening agent product shows as, acid number (mgKOHg-1)≤0.6, density (25 DEG C, gcm-3) be 0.97 ~ 1.02, oxirane value (%) >=5.0, weight loss on heating (125 DEG C × 3h, %)≤0.5%.
Embodiment 1
(1) take the cardanol of 50g, 122g epoxy chloropropane and 0.9g benzyltriethylammoinium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 98 DEG C, react 3h; After reaction terminates, be cooled to room temperature, add 6.6g solid sodium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.2g formic acid and 0.4g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 7.6g hydrogen peroxide (50%), about 0.5h drips off, and is warming up to 65 DEG C of reaction 4h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 50 DEG C or distilled water are washed till neutrality with 50 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.53, density (25 DEG C, gcm
-3): 0.99, oxirane value (%): 5.9%, weight loss on heating (125 DEG C × 3h, %): 0.5.
Embodiment 2
(1) take the cardanol of 50g, 122g epoxy chloropropane and 1.0g tetramethyl ammonium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 110 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 6.6g solid potassium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.2g acetic acid and 0.5g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 8.5g hydrogen peroxide (50%), about 0.5h drips off, and is warming up to 65 DEG C of reaction 3h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 50 DEG C or distilled water are washed till neutrality with 50 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.55, density (25 DEG C, gcm
-3): 0.98, oxirane value (%): 5.7%, weight loss on heating (125 DEG C × 3h, %): 0.5.
Embodiment 3
(1) take the cardanol of 100g, 250g epoxy chloropropane and 1.8g trimethyl benzyl ammonia chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 13.2g solid sodium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.2g formic acid and 0.6g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 6.5g hydrogen peroxide (70%), about 0.5h drips off, and is warming up to 60 DEG C of reaction 5h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 60 DEG C or distilled water are washed till neutrality with 30 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.50, density (25 DEG C, gcm
-3): 0.10, oxirane value (%): 5.8%, weight loss on heating (125 DEG C × 3h, %): 0.48.
Embodiment 4
(1) take the cardanol of 50g, 122g epoxy chloropropane and 1.1g benzyltriethylammoinium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 6.6g solid sodium hydroxide, at 65 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.0g formic acid and 0.6g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 6.5g tertbutyl peroxide, about 0.5h drips off, and is warming up to 65 DEG C of reaction 3h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 70 DEG C or distilled water are washed till neutrality with 40 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.55, density (25 DEG C, gcm
-3): 0.11, oxirane value (%): 5.6%, weight loss on heating (125 DEG C × 3h, %): 0.49.
Embodiment 5
(1) take the cardanol of 50g, 122g epoxy chloropropane, 0.5g benzyltriethylammoinium chloride and 0.5g benzyl trimethyl ammonium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 7.0g solid sodium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.5g acetic acid and 0.6g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 7.3g hydrogen peroxide (70%), about 0.5h drips off, and is warming up to 60 DEG C of reaction 5h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 50 DEG C or distilled water are washed till neutrality with 50 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.50, density (25 DEG C, gcm
-3): 0.10, oxirane value (%): 5.8%, weight loss on heating (125 DEG C × 3h, %): 0.49.
Embodiment 6
(1) take the cardanol of 50g, 102g epoxy chloropropane, 0.2g benzyl trimethyl ammonium chloride and 0.3g tetramethyl ammonium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 6.6g solid sodium hydroxide, at 50 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 10g cashew nut phenolic group glycidyl ether, 0.6g acetic acid and 0.2g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 6.5g tertbutyl peroxide, about 0.5h drips off, and is warming up to 65 DEG C of reaction 3h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 60 DEG C or distilled water are washed till neutrality with 50 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.54, density (25 DEG C, gcm
-3): 0.99, oxirane value (%): 5.2%, weight loss on heating (125 DEG C × 3h, %): 0.45.
Embodiment 7
(1) take the cardanol of 50g, 122g epoxy chloropropane and 0.9g benzyl trimethyl ammonium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 7.0g solid sodium hydroxide, at 65 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.3g acetic acid and 0.6g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 6.5g hydrogen peroxide (50%), about 0.5h drips off, and is warming up to 65 DEG C of reaction 4h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 60 DEG C or distilled water are washed till neutrality with 40 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.53, density (25 DEG C, gcm
-3): 0.99, oxirane value (%): 6.0%, weight loss on heating (125 DEG C × 3h, %): 0.50.
Embodiment 8
(1) take the cardanol of 50g, 122g epoxy chloropropane and 0.9g benzyltriethylammoinium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 95 DEG C, react 3h; After reaction terminates, be cooled to room temperature, add 6.6g solid sodium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.2g formic acid and 0.6g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 7.6g hydrogen peroxide (50%), about 0.5h drips off, and is warming up to 65 DEG C of reaction 3h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 50 DEG C or distilled water are washed till neutrality with 50 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.51, density (25 DEG C, gcm
-3): 0.99, oxirane value (%): 5.5%, weight loss on heating (125 DEG C × 3h, %): 0.5.
Embodiment 9
(1) take the cardanol of 50g, 122g epoxy chloropropane and 0.8g benzyl trimethyl ammonium chloride, add in the there-necked flask that prolong, stirring rod and thermometer are housed, at 117 DEG C, react 2h; After reaction terminates, be cooled to room temperature, add 6.6g solid sodium hydroxide, at 60 DEG C, react 3h; After filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether.
(2) 20g cashew nut phenolic group glycidyl ether, 1.2g formic acid and 0.5g tosic acid is taken, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stir and be warming up to 50 DEG C, drip 7.6g hydrogen peroxide (50%), about 0.5h drips off, and is warming up to 65 DEG C of reaction 4h; After reaction terminates, thick product obtains organic phase through stratification, be that the sodium hydrogen carbonate solution of 5% and the deionized water of 50 DEG C or distilled water are washed till neutrality with 40 DEG C of massfractions, underpressure distillation removing moisture, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product quality indicator is: outward appearance: yellow oily liquid, acid number (mgKOHg
-1): 0.50, density (25 DEG C, gcm
-3): 0.98, oxirane value (%): 6.2%, weight loss on heating (125 DEG C × 3h, %): 0.48.
After prepared softening agent and thermo-stabilizer are stirred 1min according to the formula of table 1 and PVC powder in high-speed mixer, make certain thickness PVC sheet by two roller mill, for thermostability, the test of dynamic mechanically thermal stability; And PVC sheet is obtained standardized component through cutting, injection molding, carry out tensile property test.Table 2 is Elongation test data of the PVC product of different elasticizer plasticizing, along with the increase of epoxy cashew nut phenolic group glycidyl ether plasticizer consumption, the elongation at break of goods is much larger than dioctyl phthalate (DOP) (DOP), and tensile strength is slightly larger than DOP, show this softening agent give goods better flexible while, also improve the intensity of goods, greatly can expand the range of application of goods.Dynamic thermo-mechanical property (Fig. 3) result shows that epoxy cashew nut phenolic group glycidyl ether significantly can reduce the second-order transition temperature of PVC base, has higher plasticizing efficiency.Thermal weight loss result in Fig. 4 shows, epoxy cashew nut phenolic group glycidyl ether softening agent can significantly improve the thermostability of PVC product.The volatility of PVC product, extractable and exudative test result display in Fig. 5, epoxy cashew nut phenolic group glycidyl ether has good consistency and volatility resistance, and has good acid and alkali-resistance and organic solvent-borne.
Table 1PVC article formulations
The tensile property of table 2PVC goods
Claims (10)
1. an epoxy cashew nut phenolic group glycidyl ether, it is characterized in that, raw material consists of by weight: 10 ~ 20 parts of cashew nut phenolic group glycidyl ethers, 0.5 ~ 1.5 part of organic acid, account for cardanol quality 2 ~ 3% catalyzer and 3 ~ 10 parts of peroxygen sources; Preparation method obtains cashew nut phenolic group glycidyl ether for adding highly basic ring-closure reaction again after opening by cardanol and epoxy chloropropane under opening catalyzer exists, then cashew nut phenolic group glycidyl ether again with organic acid and catalyst mix evenly and heats up afterwards that dripping peroxygen source carries out epoxidation reaction, after reaction terminates, crude product stratification, neutralization and processed, obtain finished product.
2. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 1, it is characterized in that, in described cashew nut phenolic group glycidyl ether preparation, the mass ratio of cardanol and epoxy chloropropane is 5 ~ 10:10 ~ 20, and described open loop addition catalyst accounts for 1 ~ 2% of cardanol quality.
3. the epoxy cashew nut phenolic group glycidyl ether as described in claim 1 or 2, is characterized in that, described open loop addition catalyst is one or more mixtures of benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride.
4. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 1, it is characterized in that, described highly basic is solid sodium hydroxide or solid potassium hydroxide.
5. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 1, it is characterized in that, described organic acid is formic acid or acetic acid.
6. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 1, it is characterized in that, described peroxygen source is hydrogen peroxide or tertbutyl peroxide.
7. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 6, it is characterized in that, the concentration of described hydrogen peroxide is 50% ~ 70%wt.
8. epoxy cashew nut phenolic group glycidyl ether as claimed in claim 1, it is characterized in that, described catalyzer is tosic acid.
9. the preparation method of the arbitrary described epoxy cashew nut phenolic group glycidyl ether of claim 1 ~ 8, is characterized in that,
(1) prepare cashew nut phenolic group glycidyl ether: by cardanol, epoxy chloropropane and open loop addition catalyst, at 90 ~ 120 DEG C, carry out opening 2 ~ 4 h; Continue to add highly basic and carry out ring-closure reaction 3 ~ 5 h in 50 ~ 70 DEG C; Again after filtration and underpressure distillation process, reclaim excessive epoxy chloropropane, obtain intermediate product cashew nut phenolic group glycidyl ether;
(2) epoxy cashew nut phenolic group glycidyl ether is prepared: cashew nut phenolic group glycidyl ether, organic acid and catalyzer, 3 ~ 10 g peroxygen sources are dripped in 50 DEG C, after 60 ~ 70 DEG C of reaction 3 ~ 5 h, obtain epoxy cashew nut phenolic group glycidyl ether crude product, through stratification, neutralization and processed, obtain environment-friendly epoxy cashew nut phenolic group glycidyl ether.
10. the arbitrary described epoxy cashew nut phenolic group glycidyl ether of claim 1 ~ 8 is as PVC softening agent or the application in preparation PVC softening agent.
Priority Applications (1)
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| WO2015168771A1 (en) * | 2014-05-05 | 2015-11-12 | Centre De Technologie Minerale Et De Plasturgie Inc. | Cardanol glycidyl ether derivatives |
| CN105254595A (en) * | 2015-11-08 | 2016-01-20 | 福建师范大学 | Preparation method of urushiol biglycidyl ether |
| CN105669936A (en) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | Phosphorus-containing cardanol-base polyurethane prepolymer modified phenolic foam plastic and preparation method thereof |
| CN106188617A (en) * | 2016-07-19 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of Fructus anacardii phenolic group ether type plasticizer and synthetic method thereof and application |
| CN107759711A (en) * | 2017-11-29 | 2018-03-06 | 四川大学 | Epoxy chitosan quaternary ammonium salt and preparation method thereof |
| CN111233792A (en) * | 2020-03-02 | 2020-06-05 | 上海固帮新材料科技有限公司 | Single epoxy material and preparation method thereof |
| CN111777743A (en) * | 2020-07-31 | 2020-10-16 | 中国林业科学研究院林产化学工业研究所 | Anacardic acid epoxy resin and preparation method thereof |
| CN111819234A (en) * | 2018-03-06 | 2020-10-23 | 伊士曼化工公司 | Resin composition and resin molded article |
| CN111909357A (en) * | 2019-05-08 | 2020-11-10 | 王镇 | Preparation method of water-based cardanol active emulsifier |
| CN114605259A (en) * | 2022-02-24 | 2022-06-10 | 江苏麒祥高新材料有限公司 | Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof |
| CN114805784A (en) * | 2022-02-24 | 2022-07-29 | 南京林业大学 | Preparation method of high-plasticization and anti-migration cardanol-based plasticizer |
| CN114805786A (en) * | 2022-02-24 | 2022-07-29 | 南京林业大学 | Tannin extract-based polyether polyol fatty acid ester plasticizer and preparation method and application thereof |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015168771A1 (en) * | 2014-05-05 | 2015-11-12 | Centre De Technologie Minerale Et De Plasturgie Inc. | Cardanol glycidyl ether derivatives |
| CN105254595A (en) * | 2015-11-08 | 2016-01-20 | 福建师范大学 | Preparation method of urushiol biglycidyl ether |
| CN105669936A (en) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | Phosphorus-containing cardanol-base polyurethane prepolymer modified phenolic foam plastic and preparation method thereof |
| CN105669936B (en) * | 2016-03-29 | 2018-07-13 | 中国林业科学研究院林产化学工业研究所 | A kind of phosphorous anacardol based polyurethanes performed polymer modified phenolic foam plastic and preparation method thereof |
| CN106188617A (en) * | 2016-07-19 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of Fructus anacardii phenolic group ether type plasticizer and synthetic method thereof and application |
| CN107759711A (en) * | 2017-11-29 | 2018-03-06 | 四川大学 | Epoxy chitosan quaternary ammonium salt and preparation method thereof |
| CN107759711B (en) * | 2017-11-29 | 2019-11-12 | 四川大学 | Epoxy chitosan quaternary ammonium salt and preparation method thereof |
| CN111819234A (en) * | 2018-03-06 | 2020-10-23 | 伊士曼化工公司 | Resin composition and resin molded article |
| CN111909357A (en) * | 2019-05-08 | 2020-11-10 | 王镇 | Preparation method of water-based cardanol active emulsifier |
| CN111233792B (en) * | 2020-03-02 | 2023-03-10 | 上海固帮新材料科技有限公司 | Single epoxy material and preparation method thereof |
| CN111233792A (en) * | 2020-03-02 | 2020-06-05 | 上海固帮新材料科技有限公司 | Single epoxy material and preparation method thereof |
| CN111777743A (en) * | 2020-07-31 | 2020-10-16 | 中国林业科学研究院林产化学工业研究所 | Anacardic acid epoxy resin and preparation method thereof |
| CN114805784A (en) * | 2022-02-24 | 2022-07-29 | 南京林业大学 | Preparation method of high-plasticization and anti-migration cardanol-based plasticizer |
| CN114805786A (en) * | 2022-02-24 | 2022-07-29 | 南京林业大学 | Tannin extract-based polyether polyol fatty acid ester plasticizer and preparation method and application thereof |
| CN114605259A (en) * | 2022-02-24 | 2022-06-10 | 江苏麒祥高新材料有限公司 | Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof |
| CN114805786B (en) * | 2022-02-24 | 2023-09-12 | 南京林业大学 | Tannin extract-based polyether polyol fatty acid ester plasticizer and preparation method and application thereof |
| CN114805784B (en) * | 2022-02-24 | 2023-09-12 | 南京林业大学 | Preparation method of high-plasticization and migration-resistant cardanol-based plasticizer |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
| CN116080222B (en) * | 2022-12-30 | 2024-04-05 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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