CN1025432C - Process for preparing epoxy compounds - Google Patents
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- CN1025432C CN1025432C CN 92103580 CN92103580A CN1025432C CN 1025432 C CN1025432 C CN 1025432C CN 92103580 CN92103580 CN 92103580 CN 92103580 A CN92103580 A CN 92103580A CN 1025432 C CN1025432 C CN 1025432C
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Abstract
A novel epoxy compound has a chemical structure in which an aromatic ring having a glycidyl radical attached thereto has a tertiary alkyl radical at its ortho or meta-position. An epoxy resin composition comprising the epoxy compound, a curing agent, and a curing accelerator cures into a product having a low dielectric constant.
Description
Involved in the present invention is a kind of composition epoxy resin for preparing the method for epoxy compounds and contain this epoxy compounds.
Owing to improved electrical property, bond properties and the resistance toheat of cured epoxy resin, thereby it is used as electrically insulating material, tackiness agent and coating composition widely.But because Resins, epoxy in the application in advanced field, particularly in Electrical and Electronic is used, need reach strict requirement, therefore, its resistance toheat, mechanical property and electrical property all need further to be improved.
As known formation have superior heat resistance can the example of Resins, epoxy of solidifying product ortho-cresol type novolac epoxy (EOCN) and phenol type novolac epoxy are arranged, yet still there is the fragility problem in the solidifying product of these Resins, epoxy.
Cured epoxy resin is except existing the little problem of fragility and snappiness, when improving its resistance toheat, its snappiness is further reduced, to cause many problems and lack snappiness, for example, the coating that coating composition forms is broken under the effect of surging force easily, can not reach the desired level of stripping strength when making tackiness agent, the casting thing that casting component is made also easily breaks under thermal shocking.
The known Resins, epoxy that has improved softness has polyalkylene glycol diglycidylether, lactone modified epoxy and analogue.Although flexibility improves to some extent, the cured article of these resins descends to some extent at other aspect of performance that comprises thermotolerance and physical strength.Resins, epoxy need have enough thermotolerances and flexibility, to satisfy the requirement that it is applied to advanced field.
In the veneer sheet Application Areas,, need have low specific inductivity for improving the coding rate of computer.Because the fine pattern and the compact technology of present raising computer code speed have almost reached physics limit, thereby present attention all concentrates on and inquires into another kind of method and reduce on the specific inductivity of panel material.Polyethylene and fluoro-resin are proposed as the material with low-k.But these material resin major parts have the shortcoming of low physical strength, relatively poor dimensional stability and low Copper Foil stripping strength.
Replace glass substrate also once to be considered with quartz, can seriously wear and tear but consequent problem is the drill bit of substrate perforation usefulness.
For a kind of Resins, epoxy, a prerequisite that should have is to reduce its specific inductivity, but will still keep original performance of epoxy resin.
The purpose of this invention is to provide a kind of new epoxy compound that can constitute cured epoxy resin, this cured epoxy resin and conventional Resins, epoxy relatively have lower specific inductivity, and the thermotolerance and the flexibility that have still kept improving.
Another object of the present invention provides a kind of containing with the composition epoxy resin of this epoxy compounds as fundamental component.
According to a first aspect of the invention, epoxy compounds provided here has following general formula:
Wherein n is that its value of number of repeat unit is 0～30,
R
1, R
2And R
3It is optional from hydrogen and alkyl with 1～6 carbon atom,
R
4It is a tertiary alkyl.
According to second aspect of the present invention, a kind of composition epoxy resin provided here comprises the epoxy compounds with following general formula, a kind of solidifying agent and a kind of curing catalyst.
Wherein n is that its value of number of repeat unit is 0～30,
R
1, R
2And R
3It is optional from hydrogen and alkyl with 1～6 carbon atom,
R
4It is a tertiary alkyl.
Fig. 1 and Fig. 2 show classical ring oxygen compound of the present invention
1H nucleus magnetic resonance and infrared spectrogram.
Epoxide of the present invention is a kind of compound of new chemical structure, and a tertiary alkyl is wherein arranged on the aromatic rings with glycidyl, for example, the tert-butyl group, it is preferably as shown in the molecular formula (A), on the ortho position of glycidyl.
In molecular formula (A), R1、R
2And R3Optional from hydrogen atom and the alkyl with 1～6 carbon atom. R1Preferably hydrogen or methyl, R2Preferably methyl or ethyl or propyl group, R3Preferably methyl or ethyl, particularly the place, position is connected on the aromatic rings R between the oxygen atom of adjacency4Be a tertiary alkyl, preferably the tert-butyl group particularly is connected on the aromatic rings at the place, ortho position of the oxygen atom that adjoins.
Composition epoxy resin of the present invention comprises the epoxide as the above definition of fundamental component, comprises in addition a kind of curing agent and a kind of curing accelerator. Because the steric hindrance that the tertiary alkyl in the epoxide unit causes, during so that compare with cured epoxy resin well known in the prior art, this epoxide is cured into the resin with low-k, and this resin is also improving to some extent aspect heat resistance and the flexibility.
The epoxide of molecular formula (A) can prepare by the bis-phenol in the general formula (I) and the reaction of chloropropylene oxide, and its proportioning will add 3～30 moles chloropropylene oxide for the bis-phenol of each mole.
R wherein1～R
4(A) is defined such as molecular formula. Substituent R1～R
4Preferred example and link position as previously mentioned.
This reaction can be undertaken by the whole bag of tricks of the known similar reaction of prior art. A kind of method that bis-phenol and chloropropylene oxide react is: in the situation that water exists, use a kind of alkali cpd, for example, NaOH, potassium hydroxide and lithium hydroxide, preferably use NaOH, its consumption is that the phenolic hydroxyl group of every equivalent bis-phenol is used one mole alkali cpd at least, preferably uses 1.02～1.05 moles alkali cpd, and reaction temperature is approximately 60～90 ℃. In course of reaction, etherification and dehydrohalogenation also take place simultaneously. At reaction end, from reactant mixture, remove unreacted halohydrin, water and formed salt, then the product epoxide is dry and recovery.
Also can adopt another kind of method, the method is one after the other rather than side by side to carry out etherification and dehydrohalogenation effect, and the advantage of the method is to obtain stay-in-grade epoxy resin.
Carrying out the etherification reaction stage, the about catalyst for etherification that adds 0.005～5 % by mole of the phenolic hydroxyl group of every equivalent bis-phenol is being carried out etherification reaction. Some examples of catalyst for etherification comprise tertiary amine, for example trimethylamine and triethylamine; Tertiary phosphine, for example triphenyl phasphine and three fourth phosphines; Quaternary ammonium salt, for example chlorination tetramethylammonium, bromination tetramethylammonium, chlorination triethylammonium tetrakis, Sympatektoman and Lipotril; Quaternary alkylphosphonium salt, for example bromination Si Jia Phosphonium, iodate Si Jia Phosphonium and bromination triphenyl Bing Phosphonium, and uncle's sulfonium salt, for example zephiran chloride two fourth sulfoniums and zephiran chloride diformazan sulfonium wherein adopt quaternary ammonium salt comparatively desirable. Etherification reaction goes on constantly up to about 50% at least, and preferably about at least 80% bisphenol hydroxy is by etherificate. This reaction is normally being carried out about 1～12 hour under about 60～110 ℃ temperature. Although this reaction can be carried out having in the situation of water, preferably carries out in anhydrous situation. If have water to exist, so preferably the water yield be controlled at about 3% (by weight) of reactant mixture.
In the subsequent de-hydrogen halide stage of carrying out, can from the product in etherificate stage itself, namely needn't remove unreacted epihalohydrins. Carry out this reaction in the situation of catalyst having, catalyst can be a kind of alkali cpd, alkali metal hydroxide for example, as carrying out at the same time in the method for etherificate/dehydrohalogenation, preferably use NaOH, its consumption is, for the phenolic hydroxyl group of the bis-phenol of every equivalent, the consumption of alkali cpd is at least about 0.5 mole, preferably is about 0.8 mole. For fear of disadvantageous gelatification occurring, the consumption of alkali cpd preferably defines at 1 mole.
This reaction is approximately carried out under 60～100 ℃ of temperature greatly usually 1～3 hour, when the catalyst that uses is NaOH, preferably in removing reaction system, carry out this reaction in the situation of water byproduct.
Remove unreacted epihalohydrins by the vacuum air lift then, remove by-product salt by washing, at random neutralize with weak acid, for example use phosphoric acid and sodium dihydrogen phosphate. The subsequently end product epoxides is dry and recovery.
When Zhi Bei new epoxy compound of the present invention was used for laminate like this, its epoxy equivalent (weight) heavy (EEW) was 200～2000, is preferably 230～1500, and its softening temperature is 45～130 ℃ and is preferably 55～110 ℃.
Shown below is in the new epoxy compound of the present invention an exemplary and characteristic thereof.
Title:
1, two (2-methyl-4-hydroxyl-5-tert-butyl) butane of 1-
Chemical structural formula:
Nuclear magnetic resonance spectroscopy:
Fig. 1 is this compound
1H-NMR (Nuclear Magnetic Resonance) spectrum figure.
δ (ppm) (TMS standard)
7.08 S2 proton
6.53 S2 proton
3.75～4.25 a m4 proton
3.10～3.50 a m2 proton
2.60～3.0 a m4 proton
2.20 S6 proton
0.75～2.10 a m8 proton
1.3 S18 proton
Infrared spectroscopy:
Fig. 2 is the infrared spectrogram of this compound.
The softening temperature of this compound is approximately 60 ℃.
Composition epoxy resin of the present invention comprises a kind of new epoxy compound as defined above, a kind of solidifying agent and a kind of curing catalyst.This composition epoxy resin can be cured as a kind of product of following advantage.(1) owing to reduced flowability, thereby improved the thermotolerance of this solidifying product, and mobile reduction is because R
4The huge tertiary alkyl of representative existence caused.(2) because pass through R
1, R
2And R
3It is internally plasticized that represented alkyl makes this cured product, so it is a softish.(3) because the existence of those alkyl makes this cured product that lower specific inductivity be arranged, these alkyl have R
1～R
4Represented many methyl.
The solidifying agent that is included in the composition epoxy resin of the present invention includes acid anhydrides, aromatic polyamine, aliphatic polyamine, imidazoles and phenol resins, but also is not limited only to these.
Some examples of acid anhydrides comprise, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl norbornene dioic anhydride, 1,2,4,5-pyromellitic anhydride, 1,2,4-benzenetricarboxylic anhydride, hexichol (first) ketone tetracarboxylic anhydride, dodecyl succinic anhydride and hexachloroendomethylene-tetrahvdrophthalic anhydride.
Some examples of aromatic polyamine comprise diaminodiphenylmethane, diaminodiphenylsulfone(DDS) and amine adduct.
The example of aliphatic polyamine comprise Triethylenetetramine (TETA), diethylenetriamine,
Alkene diamines, N-aminoethyl piperazine, different Fo Er copper diamines, 3, two (the 3-aminopropyls)-2,4,8 of 9-, 10-four spiral shells [5,5] undecane and amine adduct.
Some examples of phenol resins comprise resol and alkyl-substituted phenols urea formaldehyde.
Other useful solidifying agent are a Dyhard RU 100 and an xylylene amine.
Some examples of imidazoles comprise glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-ethyl-4-methylimidazole bifurcation piperazine and 1 benzyl 2 methyl imidazole.
Included curing catalyst comprises the imidazoles and the tertiary amine of following expression in composition epoxy resin of the present invention.
Some examples of imidazoles comprise glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-ethyl-4-methylimidazole bifurcation piperazine and 1 benzyl 2 methyl imidazole.
Some examples of tertiary amine comprise N, N-benzyldimethylamine and 2,4,6-three (dimethylamino methyl) phenol.
Other useful curing catalysts are 1, the octylate of 8-diaza-bicyclo-(5,4,0)+carbene-7 (it is produced by Sun Abot company, and its trade(brand)name is the commercially available product of UcatSA102), and the complex compound of single 2 basic ammonia and boron trifluoride.
Composition epoxy resin of the present invention can also comprise other epoxy compoundss of some not counterproductives of purpose that will reach said composition.The example of other epoxy compoundss of Shi Yonging has bisphenol-A epoxy compounds, bisphenol-f epoxy compounds, 1 herein, two (Racemic glycidol hydroxyphenyl) ethane of 1-, phenol phenolic aldehyde (resin) type epoxy compounds, neighbour-cresols phenolic aldehyde (resin) type epoxy compounds, glycidyl ester type epoxy compounds, glycidic amine type epoxy compounds and cyclic aliphatic epoxy compounds.When needs give solidified composition epoxy resin of the present invention with flame retardant resistance, can in composition, use tetrabromobisphenol-A-diglycidylether or be used similar fire retardant.
Work as phenol novolac epoxy resins, when particularly neighbour-cresols-novolac epoxy mixes with Resins, epoxy of the present invention, composition epoxy resin of the present invention can be more heat-resisting, its consumption is to add 0～30 part in per 100 parts of (by weight) Resins, epoxy of the present invention, preferably the phenol aldehyde type epoxy resin of 0～20 part (by weight).
In the composition epoxy resin of the present invention, except that containing above component, can also contain any one an amount of additive, for example, non-reacted thinner, as phthalic ester, (second) glycol ethers and ester class, and phenols; Reactive diluent is as long-chain alkylene oxide, butylglycidyl ether, phenyl glycidyl ether with to the monobutyl phenyl glycidyl ether; Filler is as lime carbonate, clay, asbestos, silica, mica, grinding quartz, aluminium powder, graphite, titanium oxide, alum clay, ferric oxide, glass powder and glass fibre; And tinting material, as carbon black, toluidine red, organic yellow, phthalocyanine half-sum phthalocyanine green.
The component that composition epoxy resin of the present invention comprised preferably adopts following ratio: approximately add 1～150 part in this Resins, epoxy of promptly per 100 parts (by weight), preferably the curing catalyst of the solidifying agent of 3～110 parts (by weight) and about 0.1～3 part (by weight).When solidifying agent is Dyhard RU 100, can adopt less consumption.
By with these component heat fused or in a kind of solvent the dissolved method they are mixed, prepare composition epoxy resin of the present invention like this.
Can at room temperature or be heated under about 60～250 ℃ temperature, composition epoxy resin of the present invention is cured.
Provide some embodiment below, with this as specifying to of the present invention, but the present invention is not limited to this.
With 1 of 393.8 grams, the water of two (2-methyl-4-hydroxyl-uncle 5--butylbenzene base) butane of 1-, 1221 gram Epicholorohydrins and 33 grams is injected in the reactor that agitator, reflux exchanger, dropping funnel and thermometer are housed, and then these compositions is heated to 70 ℃.When 1, after two (2-methyl-4-hydroxyl-uncle 5--butylbenzene base) butane dissolvings of 1-, again 1.2 grams being contained 53.2%(by weight) aqueous solution of chlorination tetramethylammonium joins in the above-mentioned butane solution, stirred 2 hours under 70 ℃ temperature.Then under vacuum, in the time of 70 ℃ and 2 hours, add the aqueous solution that 169.6 grams contain 48% sodium hydroxide, and during these two hours, from this reaction system, remove the water of 36.6 grams by the component distillation of Epicholorohydrin.Again distilled Epicholorohydrin is separated from water, and then it is carried back in the reaction system go.The vacuum tightness of this reaction system is controlled like this, i.e. the water yield sum that the water yield in the time per unit water yield of removing from this system sodium hydroxide solution that should equal to be added and reaction generates.
After adding the sodium hydroxide solution of above-mentioned amount, under said temperature, with reaction mixture restir 1/2 hour.So just, finished first ring-closure reaction.
Then, unreacted Epicholorohydrin and water are distilled out under vacuum.In resistates, add the mibk of 634.6 grams and the water of 377 grams.This mixture is stirred under 95 ℃ temperature, leave standstill then, be separated into organic phase and water.Sampling and remove the laggard row that desolvates and analyze from organic phase again, the concentration that records hydrolyzable chlorine be 0.58%(by weight).
Join organic phase in the reactor and be heated to 90 ℃ and add 9.8 grams then and contain 48%(by weight) aqueous solution of sodium hydroxide, it is 1.5 times of hydrolyzable chlorine molar content.Under 90 ℃ temperature, this reaction mixture was stirred 2 hours, to carry out second ring-closure reaction.End in reaction, add 70.4 grams and contain 30%(by weight) aqueous solution of SODIUM PHOSPHATE, MONOBASIC comes neutralization reaction solution, isolates organic phase again from this reaction soln.
Water component distillation from organic phase is fallen, and remove by filter inorganic salt with glass filter.Under vacuum, from filtrate, distill mibk, obtain the transparent Racemic glycidol product of 485 grams.The softening temperature of made epoxy compounds is 60 ℃, and epoxy equivalent (weight) heavily is 307 gram/equivalents, the concentration of hydrolyzable chlorine be 0.015%(by weight), number of repeat unit n is 0.27.
Inject 213.8 grams 1 in the reactor, two (2-methyl-4-hydroxyl-uncle 5--butylbenzene base) butane of 1-, 663 gram Epicholorohydrins and 21 gram water heat content then, after reaction system becomes evenly, add the aqueous solution that 1.2 grams contain 53.2% chlorination tetramethylammonium again.Under 70 ℃ temperature, continue to stir 6 hours, and then stirred 2 hours at 80 ℃.
Before beginning in second ring-closure reaction, the hydrolyzable chlorine concentration in the reaction mixture be 0.61%(by weight) outside, then the program of carrying out is identical with embodiment 1.
So just, obtain the transparent Racemic glycidol product of 247 grams, i.e. epoxy compounds, its epoxy equivalent (weight) heavily is 300 gram/equivalents, hydrolyzable chlorine concentration be 0.007%(by weight), repeating unit n is 0.24.
Embodiment 3
The preparation of composition epoxy resin: with 1 of the methylhexahydrophthalic anhydride solidifying agent (the Liqacid MH-700 that Shin-Nihon Rika K.K. Corp. makes) of the epoxy compounds that makes by embodiment 1 of 100 parts (by weight), 55 parts (by weight) and 0.5 part (by weight), 8-diaza-bicyclo-(5,4,0) undecylene-7 octanoate curing catalyst (UcatSA102 that Sun Abot company produces) mixes mutually, and then with they heating.At last said composition is cast in the plastic casting mould, solidified 1 hour at 100 ℃, 120 ℃ solidified 2 hours, and 150 ℃ solidify and solidified 4 hours in 170 ℃ in 2 hours again, just can obtain solidified Resins, epoxy.
The physicals of this cured epoxy resin sees Table 1.
Comparative Examples 1 and 2
The preparation of cured epoxy resin is to replace epoxy equivalent (weight) (weight) to be the 189(gram except the epoxy compounds that makes without embodiment 1 in Comparative Examples 1) bis phenol-a epoxy resins, the epoxy compounds that also makes without embodiment 1 in the Comparative Examples 2 and to replace epoxy equivalent (weight) (weight) be the 209(gram) (EOCN103s, Nihon Kayaku K.K. production) outside neighbour-cresol novolak epoxy, other technological processs are identical with embodiment 3.Epoxy compounds is in ratio shown in the table 1 and methylhexahydrophthalic anhydride solidifying agent and 1 in addition, and 8-diaza-bicyclo (5,4,0) undecylene-7 octanoate curing catalyst mixes mutually.
The physicals of cured epoxy resin sees Table 1.
After table 1 is seen literary composition
Embodiment 4
The preparation of homogeneous phase solution: mix the resin of 29 parts of (by weight) embodiment 1 and 20 parts of (by weight) softening temperatures and be 116 ℃, OH equivalent 214 grams/normal right-uncle-octyl phenol resol, under-150 ℃ of temperature, remove the mixture bubble.Under this temperature, 0.14 part of (by weight) glyoxal ethyline is joined in this solution.Mixture further stirs and removes bubble, and casting is advanced in the plastic casting mould then.
Mixture solidified four hours under 150 ℃ of temperature, solidified four hours in 170 ℃ again.
The resin that has solidified shows following physicals.
150 ℃ of second-order transition temperatures
Specific inductivity 2.7 during 1MHz
Dielectric loss factor 0.011 during 1MHz
Embodiment 5
The preparation of homogeneous phase solution: the softening temperature that mixes the resin of 38 parts of (by weight) embodiment and 30 parts (by weight) be 72 ℃, OH equivalent 250 grams/normal right-nonyl phenol resol, under 120 ℃ of temperature, remove the bubble of mixture.Under this temperature, 0.18 part of (by weight) glyoxal ethyline is joined in this solution.Mixture further is stirred and removes bubble, and casting is advanced in the plastic casting mould then.
Mixture solidified 3 hours at 120 ℃, and 150 ℃ solidified 2 hours, and 170 ℃ solidified 4 hours.
The resin that has solidified shows following physicals;
120 ℃ of second-order transition temperatures
Specific inductivity 2.8 during 1MHz
Dielectric loss factor 0.008 during 1MHz
Embodiment 6
The preparation of paint composite: the softening temperature that mixes the resin of 1070 parts of (by weight) embodiment 1,713 parts (by weight) equably be 116 ℃, OH equivalent 214 grams/normal right-uncle-octyl phenol resol, 10 parts of (by weight) 2-ethyl-4-methylimidazoles and 560 parts of (by weight) toluene.
The preparation of prepreg: (6232/1050/AS450 that Asahi Shuebell K.K. Corp. produces) paints the composition dipping with glass fibre, and drying just obtains prepreg then.
The making method of veneer sheet is as follows: 15 prepregs made from aforesaid method side by side are stacked together, at 10kg-f/cm
2Pressure and 180 ℃ temperature under mold pressing 60 minutes.
Prepared veneer sheet demonstrates following performance:
Resin content (weight %) 41.1
Second-order transition temperature (℃) 150 ℃
Bending strength (kg-f/mm
2) 51
Modulus in flexure (kg-f/mm
2) 1940
Specific inductivity 3.4 during 1MHz
Dielectric loss factor 0.0065 during 1MHz
Above data demonstrate significantly, and by composition epoxy resin of the present invention is solidified the cured epoxy resin that obtains, owing to mobile reduction makes it have thermotolerance, and mobile reduction is owing to the R that is connected on the phenyl ring
4Tertiary alkyl caused for representative huge.Except that thermotolerance, cured resin is because R
1, R
2And R
3The self-plasticizing action of the alkyl of representative and make it have low (bending) modulus, and be softish, again because R
1～R
4The alkyl major part of representative is a methyl and make this cured resin have low specific inductivity.
New epoxy compound of the present invention is useful to preparing a kind of composition epoxy resin, and bisphenol-A type Resins, epoxy and neighbour-cresol novolak epoxy than routine after this composition epoxy resin solidifies have gratifying resistance toheat, softness and low specific inductivity.
The solidifying product made from composition epoxy resin of the present invention has extraordinary heat impedance in the Electrical and Electronic field during as sealing material or insulating coating, and is applied to multiple use with the cured epoxy resin with minimum fragility and low-k.
According to the above, can see significantly that it is possible that the present invention is carried out some modifications and changes.What therefore need explanation a bit is that in additional claim scope, the present invention can adopt the method that is different from qualification herein to implement.
Table 1
E3 CE1 CE2
Composition umber (by weight)
Epoxy compounds
Comparative Examples 1-100-
Comparative Examples 2--100
Solidifying agent 55 86 75
Curing catalyst 0.5 0.5 0.5
Solidify physicals
Second-order transition temperature
* 1(℃) 178 156 186
Bending strength
* 2(kg-f/mm
2) 12.8 13.0 12.8
Modulus in flexure
* 2(kg-f/mm
2) 260 290 340
Specific inductivity
* 2During 1KHZ 2.9 3.3 3.4
During dielectric loss factor 1KHZ 0.0104 0.007-
* 1The difference scanning calorimeter
* 2The K6911 of Japanese Industrial Standards (JIS).
Claims (1)
1, the method for the epoxy compounds of a kind of preparation formula (A) comprising:
Bis-phenol and Epicholorohydrin are reacted, and its ratio is that every mole of bis-phenol adds 3 to 30 moles Epicholorohydrin,
Wherein bis-phenol can be represented with formula I:
Wherein n is a number of repeat unit, and its numerical value is 0-5,
R
1Be hydrogen,
R
2Be n-propyl,
R
3Be methyl and
R
4It is the tertiary butyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92103580 CN1025432C (en) | 1987-05-29 | 1992-05-12 | Process for preparing epoxy compounds |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13439387 | 1987-05-29 | ||
| JP134393/87 | 1987-05-29 | ||
| CN88104252A CN1021048C (en) | 1987-05-29 | 1988-05-28 | Epoxy resin composition |
| CN 92103580 CN1025432C (en) | 1987-05-29 | 1992-05-12 | Process for preparing epoxy compounds |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104252A Division CN1021048C (en) | 1987-05-29 | 1988-05-28 | Epoxy resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN1066846A CN1066846A (en) | 1992-12-09 |
| CN1025432C true CN1025432C (en) | 1994-07-13 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92103580 Expired - Fee Related CN1025432C (en) | 1987-05-29 | 1992-05-12 | Process for preparing epoxy compounds |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061665C (en) * | 1998-05-01 | 2001-02-07 | 巴陵石化岳阳石油化工总厂 | Cast epoxy resin for high-voltage switch and its preparation |
| CN1073581C (en) * | 1998-09-04 | 2001-10-24 | 巴陵石化岳阳石油化工总厂 | Injection epxoy resin for high voltage switch and its mfg. method |
| EP1885678A1 (en) * | 2005-05-20 | 2008-02-13 | Solvay S.A. | Continuous method for making chlorhydrines |
| CN100393708C (en) * | 2005-06-23 | 2008-06-11 | 中国科学院化学研究所 | Fluoro epoxide and its preparation method and use |
| CN101794976A (en) * | 2010-03-12 | 2010-08-04 | 扬中市江城电器设备有限公司 | High-voltage resistant waterproof bus duct for wind power/nuclear power/water power and manufacturing method thereof |
| CN108203418B (en) * | 2016-12-20 | 2021-09-03 | 上海朗亿功能材料有限公司 | Epoxy modified monocarbodiimide compound and preparation method thereof |
| CA3047399A1 (en) * | 2016-12-21 | 2018-06-28 | Huntsman Advanced Materials Licensing (Switzerland) Gmbh | Latent curing accelerators |
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