CN109096228A - A kind of preparation method and applications of Dipentenedioxide - Google Patents
A kind of preparation method and applications of Dipentenedioxide Download PDFInfo
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- CN109096228A CN109096228A CN201810873187.4A CN201810873187A CN109096228A CN 109096228 A CN109096228 A CN 109096228A CN 201810873187 A CN201810873187 A CN 201810873187A CN 109096228 A CN109096228 A CN 109096228A
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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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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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
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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Abstract
The invention discloses a kind of preparation method and applications of Dipentenedioxide, raw materials used preparation method includes: limonene 10%~12%, toluene 40%~45%, aceticanhydride 18%~22%, sodium acetate 5%~8%, hydrogenperoxide steam generator 17%~20%；The quality sum of above-mentioned each raw material component is 100%；The percentage is mass percent.Dipentenedioxide high income that the present invention is prepared, selectivity are high, the purity is high of reaction product, it is a kind of outstanding epoxide resin reactive diluent, on the glass transition temperature of epoxy resin cured product almost without influence in the solidification process of main body epoxy resin, and it is hot under mechanical strength conservation rate it is higher, alkali resistance is good.
Description
Technical field
The present invention relates to a kind of preparation method and applications of Dipentenedioxide, belong to the dilution of neo-epoxy resin activity
Agent field.
Background technique
The mobility of epoxy resin compound is very important the purposes such as coating, casting, encapsulating.To adapt to this
The requirement of a little aspects, many times needs to reduce system viscosity.Diluent is mainly used to reduce the viscous of epoxy-resin systems
Degree, dissolution, dispersion and dilution coating, improves the coating and mobility of glue.But after addition diluent can also reduce solidification
The heat distortion temperature of resin, glue-joint strength, media-resistant and the performances such as ageing-resistant.However, in order to make resin adhesive liquid be easy to infiltrate glue
The surface for closing object, improves its wetting capacity and wetting power, convenient for operation, and must be added to suitable diluent.
Existing is commonly non-activated thinner (being free of epoxy group, do not react with epoxy resin, curing agent etc.), it
It is largely vapored away in the solidification process of glue, many holes can be left to resin cured matter, make cure shrinkage phase
To increase.Therefore, non-activated thinner is larger to the adverse effect of resin property after solidification, cannot make when requirement is higher
Use non-activated thinner.
Summary of the invention
The present invention provides a kind of preparation method and applications of Dipentenedioxide, passes through the epoxy and ring-type of products obtained therefrom
Structure guarantees on the glass transition temperature of epoxy resin cured product almost without influence, and hot lower mechanical strength conservation rate height, resistance to
Chemicals are good.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of preparation method of Dipentenedioxide, it is raw materials used to include:
The quality sum of above-mentioned each raw material component is 100%；The percentage is mass percent.
The main function of above-mentioned sodium acetate is that the pH value of adjusting reaction system is conducive to using sodium acetate regulating system pH
The progress of reaction and the raising of conversion ratio.And aceticanhydride reacts with hydrogen peroxide and generates Peracetic acid, plays catalytic oxidation jointly
Effect.Applicant it has been investigated that, the above method not only makes the yield of product and selectivity be improved significantly, and to epoxy
The glass transition temperature and mechanical strength conservation rate of resin are high, and chemical-resistant is good.
In order to guarantee product quality and reaction process safety, the mass concentration 40-50% of hydrogenperoxide steam generator.
The preparation method of above-mentioned Dipentenedioxide, including the following steps being connected in order:
(1) limonene, toluene, aceticanhydride and sodium acetate are mixed, is subsequently cooled to no more than 15 DEG C；
(2) hydrogen peroxide is added in step (1) resulting material and is reacted；
(3) pH of step (2) resulting material is adjusted to alkalinity, stratification leaves and takes upper organic phase；
(4) sodium sulfite aqueous solution being added into step (3) resulting organic phase, stratification obtains upper organic phase,
Organic phase precipitation recycling toluene is obtained into crude product；
(5) by the resulting crude product rectification and purification of step (4), Dipentenedioxide is obtained.
It is preferred that being cooled to 5 DEG C -15 DEG C in step (1).It is cooled in the temperature range and hydrogen peroxide is added dropwise, reaction temperature is easy
It controls and side reaction is few；Because hydrogen peroxide oxidation is strong, reaction is exothermic reaction, to react under 5-15 DEG C of low temperature environment
It steadily can lenitively carry out, prevent initial reaction stage heat release is excessively violent, temperature raising is too fast to be difficult to control, so as to cause production
Security risk.
In order to reduce side reaction, the stability of reaction is improved, improves the yield and selectivity of products obtained therefrom, it is preferable that step
(2) are as follows: instill 50% hydrogen peroxide in step (1) resulting material, control temperature of reaction system is 15 DEG C -25 DEG C, is added dropwise
2-3 hours；After being added dropwise, at 15 DEG C -25 DEG C, the reaction was continued 3-6 hours.
Since Peracetic acid is a kind of extremely unstable strong oxidizer, -20 DEG C also can vigorous reaction, concentration is greater than 45%
When just have explosion danger；The application is reacted using aceticanhydride with hydrogen peroxide, by control metering and rate of addition, makes to generate peroxide second
The concentration and speed of acid are controllable, substantially reduce security risk, guarantee that reacting balance carries out.
System temperature and time for adding control are in above range, it can be ensured that react safety and steady and efficiently carry out；Temperature
Height, time short then reaction are acutely uncontrollable, and temperature is low, time long then reaction speed is too slow, and production efficiency is low.
It is preferred that the pH of step (2) resulting material is adjusted to 10-12 in step (3).PH be adjusted to the range more added with
Conducive to the progress of reaction and the raising of conversion ratio.
In order to reduce side reaction, the stability of reaction is improved, improves the yield and selectivity of products obtained therefrom, it is preferable that step
(3) are as follows: the pH of step (2) resulting material is adjusted to 10-12 by the NaOH solution for being 20-40% with mass fraction, stirs 10-30
Stratification after minute, leaves and takes upper organic phase.
In order to improve the yield and selectivity of products obtained therefrom, guarantee the performance of products obtained therefrom, step (4) are as follows: to step (3)
The sodium sulfite aqueous solution that mass concentration is 10-15% is added in resulting organic phase, after stirring 10-30 minutes, stratification,
Upper organic phase is obtained, organic phase precipitation recycling toluene is obtained into crude product；
Dipentenedioxide obtained by above-mentioned preparation method can directly participate in epoxy resin as reactive diluent
Curing reaction becomes a part of epoxy resin cured product cross-linked network structure, substantially improves glue-line performance, to the machine of solidfied material
Tool performance etc. can also increase the toughness of curing system almost without influence sometimes, reduce and shrink.
As reactive diluent in use, the quality dosage of Dipentenedioxide is the 10 ± 2% of epoxy resin quality.
The unmentioned technology of the present invention is referring to the prior art.
Dipentenedioxide high income that the present invention is prepared, selectivity are high, the purity is high of reaction product, are a kind of excellent
Elegant epoxide resin reactive diluent, to the glass transition temperature of epoxy resin cured product in the solidification process of main body epoxy resin
Almost without influence, and it is hot under mechanical strength conservation rate it is higher, alkali resistance is good.
Detailed description of the invention
Fig. 1 is the C13 nmr spectrum of 1 gained Dipentenedioxide of embodiment.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
50% hydrogen peroxide used in each example is the technical grade top grade purchased from Guangzhou Hai Ying Biotechnology Co., Ltd
Product, the mass content of hydrogen peroxide are 50%.
Embodiment 1
The preparation method of Dipentenedioxide, includes the following steps:
(1) 300g limonene, 1200g toluene, 540g aceticanhydride and 185g sodium acetate are added into 2000ml three-necked flask, stirs
It mixes and is cooled to 5 DEG C -10 DEG C under state；
(2) then start that 50% hydrogen peroxide of 498g is added dropwise, control rate of addition keeps temperature of reaction system to be no more than 25
DEG C, it is added dropwise within about 2 hours, the reaction was continued after completion of dropwise addition 5 hours；
(3) it is slowly added to the NaOH solution that 125g mass concentration is 32% into system and adjusts pH to 10-12, stirs 10 points
Clock stands split-phase, separates upper organic phase；
(4) sodium sulfite aqueous solution that 80g mass concentration is 10% is added into organic phase, stirs to stand for 10 minutes and divide
Phase separates upper organic phase (pH=10-12, starch potassium iodide paper show no peroxide residual), and precipitation recycling toluene obtains
To crude product；
(5) rectifying purifying being carried out to crude product, collects purity in 95% or more fraction 276g, product yield reaches 92%,
Selectivity 99%, epoxide equivalent 92g/eq, 25 DEG C of viscosity 7.6mPas.
The C13 nmr spectrum of products obtained therefrom is as shown in Figure 1, structural formula are as follows:
Embodiment 2
The preparation method of Dipentenedioxide, includes the following steps:
(1) 240g limonene, 960g toluene, 412g aceticanhydride and 141.4g sodium acetate are added into 2000ml three-necked flask,
10 DEG C -15 DEG C are cooled under stirring；
(2) then start that the hydrogen peroxide that 380g mass concentration is 50% is added dropwise, control rate of addition keeps reaction system
Temperature is no more than 25 DEG C, is added dropwise within about 2 hours, the reaction was continued after completion of dropwise addition 6 hours；
(3) it is slowly added to the NaOH solution that 95g mass concentration is 32% into system and adjusts pH to 10-12, stirs 10 points
Clock stands split-phase, separates upper organic phase；
(4) sodium sulfite aqueous solution that 60g mass concentration is 10% is added into organic phase, stirs to stand for 10 minutes and divide
Phase separates upper organic phase (pH=10-12, starch potassium iodide paper show no peroxide residual), and precipitation recycling toluene obtains
To crude product；
(5) rectifying purifying being carried out to crude product, collects purity in 95% or more fraction 216g, product yield reaches 90%,
Selectivity 98.5%, epoxide equivalent 92.5g/eq, 25 DEG C of viscosity 7.7mPas.
The C13 nmr spectrum of products obtained therefrom is identical with embodiment 1, therefore does not repeat to provide.
Embodiment 3
The preparation method of Dipentenedioxide, includes the following steps:
(1) 270g limonene, 1080g toluene, 501g aceticanhydride and 171.2g sodium acetate are added into 2000ml three-necked flask,
5 DEG C -10 DEG C are cooled under stirring；
(2) then start that the hydrogen peroxide that 460g mass concentration is 50% is added dropwise, control rate of addition keeps reaction system
Temperature is no more than 25 DEG C, is added dropwise within about 2.5 hours, the reaction was continued after completion of dropwise addition 4.5 hours；
(3) it is slowly added to the NaOH solution that 115.5g mass concentration is 32% into system and adjusts pH to 10-12, stirring 10
Minute stands split-phase, separates upper organic phase；
(4) sodium sulfite aqueous solution that 74g mass concentration is 10% is added into organic phase, stirs to stand for 10 minutes and divide
Phase separates upper organic phase (pH=10-12, starch potassium iodide paper show no peroxide residual), and precipitation recycling toluene obtains
To crude product；
(5) rectifying purifying being carried out to crude product, collects purity in 95% or more fraction 243g, product yield reaches 90%,
Selectivity 99%, epoxide equivalent 91.5g/eq, 25 DEG C of viscosity 7.5mPas.
The C13 nmr spectrum of products obtained therefrom is identical with embodiment 1, therefore does not repeat to provide.
Comparative example 1
A kind of preparation method of Dipentenedioxide, includes the following steps:
(1) 300g limonene, 1200g dichloroethanes, 540g aceticanhydride and 185g acetic acid are added into 2000ml three-necked flask
Sodium is cooled to 5 DEG C -10 DEG C under stirring；
(2) then start that the hydrogen peroxide that 498g mass concentration is 50% is added dropwise, control rate of addition keeps reaction system
Temperature is no more than 25 DEG C, is added dropwise within about 2 hours, the reaction was continued after completion of dropwise addition 5 hours；
(3) it is slowly added to the NaOH solution that 125g mass concentration is 32% into system and adjusts pH to 10-12, stirs 10 points
Clock stands split-phase, separates upper organic phase；
(4) sodium sulfite aqueous solution that 80g mass concentration is 10% is added into organic phase, stirs to stand for 10 minutes and divide
Phase separates upper organic phase (pH=10-12, starch potassium iodide paper show no peroxide residual), and precipitation recycling toluene obtains
To crude product；
(5) rectifying purifying being carried out to crude product, collects purity in 95% or more fraction 255g, product yield reaches 85%,
Selectivity 98%, epoxide equivalent 93g/eq, viscosity 8.0mPas.
Comparative example 2
A kind of preparation method of Dipentenedioxide, includes the following steps:
(1) 240g limonene, 960g toluene, 412g aceticanhydride and 91.4g sodium carbonate are added into 2000ml three-necked flask, stirs
It mixes and is cooled to 10 DEG C -15 DEG C under state；
(2) then start that the hydrogen peroxide that 380g mass concentration is 50% is added dropwise, control rate of addition keeps reaction system
Temperature is no more than 25 DEG C, is added dropwise within about 2 hours, the reaction was continued after completion of dropwise addition 6 hours；
(3) it is slowly added to the NaOH solution that 95g mass concentration is 32% into system and adjusts pH to 10-12, stirs 10 points
Clock stands split-phase, separates upper organic phase；
(4) sodium sulfite aqueous solution that 60g mass concentration is 10% is added into organic phase, stirs to stand for 10 minutes and divide
Phase separates upper organic phase (pH=10-12, starch potassium iodide paper show no peroxide residual), and precipitation recycling toluene obtains
To crude product；
(5) rectifying purifying being carried out to crude product, collects purity in 95% or more fraction 211g, product yield reaches 88%,
Selectivity 95%, epoxide equivalent 93.5g/eq, viscosity 8.2mPas.
Comparative example 3
Solvent toluene is taken, as non-activated thinner (being free of epoxy group), according to the formula composition of table 1, is prepared solid
The property changed resin combination does performance evaluation test according to above-mentioned identical condition of cure after solidification.
The product that the above various embodiments and comparative example are prepared, as diluent, and according to the formula composition of table 1,
A series of hardening resin compositions are prepared, according to identical condition of cure, performance evaluation test is done after solidification.Wherein, have
The condition of cure of body is 120 DEG C × 2.5h+150 DEG C × 2.5h.
Table 1 (numerical value is mass fraction in table)
Note: epoxy resin is general bisphenol A epoxide resin (trade mark YD-128, national capital resin, epoxide equivalent 190g/ in table
Eq, viscosity 13000mPas)；Diluent is each embodiment or comparative example resulting product；Curing agent is methyl hexahydrophthalic anhydride
(Jiaxing Qing Yang, anhydride equivalent 168g/mol, viscosity 50mPas)；Promotor is N, (the US Air gasification of N- dimethyl benzylamine
Work).
The performance evaluation of above-mentioned each application examples is tested, and is carried out according to following operating method.
(1) viscosity test is mixed
According to standard GB/T 10247-2008, the mixing viscosity test of hardening resin composition is carried out.
(2) glass transition temperature (Tg) is tested
According to standard ISO11357-2, the test of solidfied material glass transition temperature Tg is carried out.
(3) bending strength is tested
According to standard ASTM D790, (85 DEG C) progress bending strength tests under (25 DEG C) and high temperature at normal temperature respectively, and
It calculates hot strength conservation rate (85 DEG C).
(4) alkali resistance is evaluated
For each application examples, in the evaluation testing piece made of glass plate, 1%NaOH aqueous solution is added dropwise dropwise, and
It places 10 minutes.Then, testing piece surface is cleaned with pure water, observes result after drying.
The NaOH aqueous solution place of dripping is completely unconverted to be denoted as √, only remains a small amount of solvent trace and can disappear after wiping
That loses is denoted as O, remains compared with multi-solvent trace and what is do not disappeared after wiping is denoted as △, and what whole surface changed colour be denoted as ×.
The result of each resulting condensate performance evaluation test of example is listed in table 2.
Table 2
It is by 2 evaluation test result of table it is found that obtained using each embodiment and comparative example (embodiment 1-3, comparative example 1-2)
Product Dipentenedioxide, as active epoxy diluent, the solidfied material glass transition temperature being prepared is higher, bending strength compared with
By force, the strength retention under especially hot is high (85 DEG C ,~80%), and alkali resistance is good, and it is lower that resin combination mixes viscosity, stream
Dynamic property is good；And be substantially reduced using the solidfied material glass transition temperature that non-activated thinner (comparative example 3) is prepared, it is hot lower strong
Degree conservation rate is low (85 DEG C, < 30%), and alkali resistance is poor, since non-activated thinner is free of epoxy group, reacts required curing agent
Amount is few, therefore the mixing viscosity of resin combination is slightly higher, and mobility is slightly worse；The test result of embodiment 1-3 is significantly better than comparison
Example 1-2.
Claims (10)
1. a kind of preparation method of Dipentenedioxide, it is characterised in that: raw materials used to include:
The quality sum of above-mentioned each raw material component is 100%；The percentage is mass percent.
2. preparation method as described in claim 1, it is characterised in that: the mass concentration 40-50% of hydrogenperoxide steam generator.
3. preparation method as claimed in claim 1 or 2, it is characterised in that: including the following steps being connected in order:
(1) limonene, toluene, aceticanhydride and sodium acetate are mixed, is subsequently cooled to no more than 15 DEG C；
(2) hydrogen peroxide is added in step (1) resulting material and is reacted；
(3) pH of step (2) resulting material is adjusted to alkalinity, stratification leaves and takes upper organic phase；
(4) sodium sulfite aqueous solution is added into step (3) resulting organic phase, stratification obtains upper organic phase, will have
Machine phase precipitation recycling toluene obtains crude product；
(5) by the resulting crude product rectification and purification of step (4), Dipentenedioxide is obtained.
4. preparation method as claimed in claim 3, it is characterised in that: in step (1), be cooled to 5 DEG C -15 DEG C.
5. preparation method as claimed in claim 3, it is characterised in that: step (2) are as follows: 50% hydrogen peroxide is instilled step
(1) in resulting material, control temperature of reaction system is 15 DEG C -25 DEG C, is added dropwise 2-3 hours；After being added dropwise, at 15 DEG C -25
At DEG C, the reaction was continued 3-6 hours.
6. preparation method as claimed in claim 3, it is characterised in that: in step (3), by the pH tune of step (2) resulting material
It saves to 10-12.
7. preparation method as claimed in claim 6, it is characterised in that: step (3) are as follows: with mass fraction be 20-40%'s
The pH of step (2) resulting material is adjusted to 10-12 by NaOH solution, and it is organic to leave and take upper layer for stratification after stirring 10-30 minutes
Phase.
8. preparation method as claimed in claim 3, which is characterized in that step (4) are as follows: into step (3) resulting organic phase
The sodium sulfite aqueous solution that mass concentration is 10-15% is added, after stirring 10-30 minutes, it is organic to obtain upper layer for stratification
Organic phase precipitation recycling toluene is obtained crude product by phase.
9. Dipentenedioxide conduct obtained by the preparation method of Dipentenedioxide described in claim 1-8 any one
The application of epoxy active diluent.
10. application as claimed in claim 9, it is characterised in that: the quality dosage of Dipentenedioxide is epoxy resin quality
10 ± 2%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183401A (en) * | 2019-06-27 | 2019-08-30 | 江苏泰特尔新材料科技有限公司 | A kind of synthesis technology for the di-epoxide that safety and environmental protection is controllable |
| CN110591054A (en) * | 2019-09-17 | 2019-12-20 | 江苏泰特尔新材料科技有限公司 | Epoxide with low total chlorine content and no heavy metal residue and synthesis process thereof |
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| WO2017215929A1 (en) * | 2016-06-15 | 2017-12-21 | BASF Agro B.V. | Process for the epoxidation of a tetrasubstituted alkene |
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| US3130207A (en) * | 1960-11-03 | 1964-04-21 | Fmc Corp | Improved epoxidation process with liquid aliphatic peroxy acids |
| RU2324690C1 (en) * | 2006-10-31 | 2008-05-20 | Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН (НИОХ СО РАН) | Method of production of limonene diepoxides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110183401A (en) * | 2019-06-27 | 2019-08-30 | 江苏泰特尔新材料科技有限公司 | A kind of synthesis technology for the di-epoxide that safety and environmental protection is controllable |
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| CN110591054A (en) * | 2019-09-17 | 2019-12-20 | 江苏泰特尔新材料科技有限公司 | Epoxide with low total chlorine content and no heavy metal residue and synthesis process thereof |
| CN110591054B (en) * | 2019-09-17 | 2021-05-18 | 江苏泰特尔新材料科技股份有限公司 | Epoxide with low total chlorine content and no heavy metal residue and synthesis process thereof |
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Application publication date: 20181228 |