CN1203103C - Naphthyl type epoxy resin and its preparing method - Google Patents
Naphthyl type epoxy resin and its preparing method Download PDFInfo
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- CN1203103C CN1203103C CN 03113923 CN03113923A CN1203103C CN 1203103 C CN1203103 C CN 1203103C CN 03113923 CN03113923 CN 03113923 CN 03113923 A CN03113923 A CN 03113923A CN 1203103 C CN1203103 C CN 1203103C
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- epoxy
- dinaphthalene
- dihydroxyl
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- epoxy chloropropane
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- 125000001624 naphthyl group Chemical group 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 title abstract description 15
- 239000003822 epoxy resin Substances 0.000 title abstract description 13
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims description 69
- 229920005989 resin Polymers 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000006266 etherification reaction Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 150000002790 naphthalenes Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AJARGPYJMXPADH-UHFFFAOYSA-N 1,1'-biphenyl methanediamine Chemical compound NCN.C1(=CC=CC=C1)C1=CC=CC=C1 AJARGPYJMXPADH-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The present invention relates to novel naphthyl type epoxy resin and a preparing method thereof. The epoxy resin has a molecular formula I. In preparing method, a one-step method can be adopted, namely that a mixture of 2, 2'-dihydroxyl-1, 1'-dinaphthalene and epoxy chloropropane is directly condensed under the action of alkali to obtain the epoxy resin; a two-step method can also be adopted, namely that 2, 2'-dihydroxyl-1, 1'-dinaphthalene and epoxy chloropropane are firstly etherified under the action of catalysts and then are cyclized under the action of alkali solution to obtain the epoxy resin. The present invention also provides a solidified product of the naphthyl type epoxy resin. The glass transition temperature of the solidified product generated by the epoxy resin under the action of a general solidifying agent is higher than 140 DEG C and also has high mechanical strength and low fusing viscosity, so that the solidified product has a favorable processing property.
Description
Technical field
The present invention relates to a kind of novel naphthyl type Resins, epoxy and preparation method thereof.
Technical background
Resins, epoxy (epoxy resins) is meant and contains two above epoxy group(ing) in the molecule, and in the presence of suitable chemical reagent (solidifying agent), can form the general name of the compound of three-dimensional crosslinked network shape cured article, be one of most important kind in the thermoset macromolecule material.Because epoxy resin cured product has good chemical stability, electrical insulating property, erosion resistance, cohesiveness and physical strength, so it is widely used in fields such as chemical industry, electronics, electrical equipment, water conservancy, traffic and space flight and aviation.The important use of Resins, epoxy in the electric and electronic industry is the packaged material as semi-conductor electronic device.Because electronics, electrical equipment industry develop rapidly, technology innovation is very rapid, therefore be faced with the problem of high performance for its supporting epoxide resin material, an important directions of the high performance of Resins, epoxy is to improve the thermotolerance and the wet fastness of resin cured matter, and reduces the internal stress of cured article.
According to the requirement of macromolecular material structure and property relationship principle and epoxy resin high-performanceization, people have carried out many-sided research to the molecular structure and the property relationship of Resins, epoxy in recent years.Synthetic and the performance of heat resistant type Resins, epoxy has become one of the focus of the research of macromolecular material.From the structure and the performance principle of macromolecular material, improve the thermotolerance of Resins, epoxy and generally start with: the rigidity that 1) improves the Resins, epoxy molecular backbone chain from the following aspects; 2) introduce stable on heating skeleton at the Resins, epoxy molecular backbone chain; 3) resin of synthetic polyfunctionality, thereby cross-linking density when increasing resin solidification.
According to above principle, scientific research personnel people synthesize many novel stable on heating Resins, epoxy that have in recent years, integrate and mainly contain following a few class: phenolic aldehyde epoxy, alicyclic epoxy, aromatic epoxies.Aromatic epoxies mainly contains bisphenol S type epoxy, and biphenyl type epoxy contains the Resins, epoxy of fragrant heterocycle structure etc.In the synthetic and performance study work of new aromatic epoxy compounds, the synthetic of Resins, epoxy that contains naphthalene nucleus attracted attention the most, and naphthyl Resins, epoxy is to be raw material with naphthols or naphthalenediol, synthetic under the effect of catalyzer.This resinoid has good thermotolerance and water tolerance, has broad application prospects.At present, about naphthalene be the report of Resins, epoxy mostly from Japan of electronic industry prosperity, they mainly are as the electric and electronic material.Naphthalene is that the most representative product of Resins, epoxy is nineteen eighty-three, and rugged Longde, Pu utilizes naphthyl alcohol and formalin polymerization, synthesizes the naphthol novolac resin of line style, naphthol novolac epoxy resin therefrom again:
Such naphthalene is that epoxy has been introduced the naphthalene nucleus that rigidity is big, hydrophobicity is strong owing on the main chain, so can keep superior heat resistance, can reduce water-absorbent again.It is reported that this resin has the second-order transition temperature height, the good characteristic that water-intake rate is low, but this resin is solid at normal temperatures, the fusing point height, and viscosity is big, and poor processability has limited its use.In recent years, many researchists are doing a few thing aspect its modification, have obtained certain progress, but it is promoted the use of and needs time.
Summary of the invention
The purpose of this invention is to provide a kind of naphthyl type Resins, epoxy, this naphthyl type Resins, epoxy is owing to the hydrophobicity of having introduced high inflexible dinaphthalene ring structure and naphthalene nucleus on the main chain is strong, so can keep superior heat resistance, can reduce water-absorbent again, compare with the naphthol novolac epoxy resin of having reported, owing to be semi-solid at normal temperatures, and melt viscosity is extremely low, therefore has the better processability energy.
Another object of the present invention provides the preparation method of this naphthyl type Resins, epoxy.
Also purpose of the present invention provides the cured product of this naphthyl type Resins, epoxy.
Naphthyl type Resins, epoxy provided by the invention is with 2,2 '-dihydroxyl-1, and 1 '-dinaphthalene, epoxy chloropropane are raw material, under the effect of alkali, obtain Resins, epoxy:
Novel naphthyl type Resins, epoxy provided by the invention, its molecular formula is:
n＝0，1，2......28
This resin oxirane value: 0.02～0.50, outward appearance is pale brown look semi-solid attitude to solid-state (under the normal temperature) with the oxirane value difference.
Preferred n=0～5, oxirane value 0.1～0.50.
A kind of method for preparing this novel naphthyl type Resins, epoxy is to adopt single stage method; promptly 2; 2 '-dihydroxyl-1; the mixture of 1 '-dinaphthalene and epoxy chloropropane directly under the effect of alkali condensation obtain Resins, epoxy; concrete steps are: with 2; 2 '-dihydroxyl-1,1 '-dinaphthalene and epoxy chloropropane be by 1: 6～20 mixed in molar ratio, under protection of inert gas 80～120 ℃ of reacting by heating 2～3 hours; drip strong base solution simultaneously; highly basic and 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene is 1.04～2: 1; the reaction finish after after filtration; washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.
Wherein used highly basic can adopt sodium hydroxide, potassium hydroxide etc.Used strong base solution is preferably selected denseer solution for use, and the preferential concentration of selecting is between 20～50wt%.
2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane preferred 1: 6～15.
Highly basic and 2,2 '-dihydroxyl-1, preferred 2: 1 of the mol ratio of 1 '-dinaphthalene.
The method of another kind of this novel naphthyl type Resins, epoxy of preparation is to adopt two step method, promptly at first 2,2 '-dihydroxyl-1,1 '-dinaphthalene and epoxy chloropropane be etherificate under the effect of catalyzer, closed loop obtains Resins, epoxy under the effect of alkali lye then, specifically may further comprise the steps:
(1), under protection of inert gas, 2,2 '-dihydroxyl-1, add doped quaternary ammonium salt in 1 '-dinaphthalene and the epoxy chloropropane and make catalyzer, 80～120 ℃ down heating carried out etherification reaction 1～4 hour, wherein 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane are 1: 6～20;
(2), etherification reaction finishes back dropping strong base solution and carries out ring-closure reaction, reacted 1～3 hour down at 100～120 ℃, by mole, the alkaline add-on is 2,2 '-dihydroxyl-1,2～2.5 times of 1 '-dinaphthalene, the reaction finish after after filtration, washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.
Wherein in the step (1), 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane can be between 1: 6～20, and preferred 1: 6～12.
The catalyzer doped quaternary ammonium salt can be selected from benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetraethylammonium bromide, 4 bromide etc.
Highly basic used in the step (2) can adopt sodium hydroxide, potassium hydroxide etc.Used strong base solution is preferably selected denseer solution for use, and the preferential concentration of selecting is between 20～50wt%.Highly basic and 2,2 '-dihydroxyl-1, preferred 2: 1 of the mol ratio of 1 '-dinaphthalene.
The present invention also provides the cured product of this naphthyl type Resins, epoxy.
The curing of Resins, epoxy has nothing different in the curing of this naphthyl type Resins, epoxy and the prior art, solidifying agent commonly used in the prior art all is suitable for, as the fatty amine in the polyamine, cycloaliphatic amines, aromatic amine and modified multicomponent amine, acid anhydrides, tertiary amine, imidazoles, BF
3Complex compound etc.
Synthesize the Resins, epoxy that obtains by the present invention and adopt mphenylenediamine, phenylbenzene diamino methane, Dicyanodiamide etc. to be cured, table 1 has been listed the thermal characteristics and the mechanical property of corresponding cured article:
Table 1: the thermal characteristics of epoxy resin cured product of the present invention and mechanical property
| Oxirane value | 0.3696 | 0.4015 | 0.4353 |
| Solidifying agent | Mphenylenediamine | Dicyanodiamide | Phenylbenzene diamino methane |
| Glass transition temperature Tg (℃) | 153.69℃ | 147.52℃ | 163.54℃ |
| Ultimate compression strength (MPa) | 87.6 | 68.7 | 90.5 |
As the thermosetting epoxy resin material, it is generally acknowledged that its cured article second-order transition temperature of high heat resistance (Tg, ℃) should be at least greater than 140 ℃.As can be seen from the above table, the present invention synthesizes the Resins, epoxy that obtains, and it solidifies the glass transition temperature all greater than 140 ℃ under solidifying agent commonly used, and also has higher mechanical strength, has therefore reached the purpose of invention novel high-performance heat resistant type Resins, epoxy.
Naphthyl type Resins, epoxy provided by the invention is owing to the hydrophobicity of having introduced high inflexible dinaphthalene ring structure and naphthalene nucleus on the main chain is strong, so can keep superior heat resistance, can reduce water-absorbent again, compare with the naphthol novolac epoxy resin of having reported, melt viscosity is extremely low, especially n=0～5, this naphthyl Resins, epoxy of oxirane value 0.1～0.50 is semi-solid attitude at normal temperatures, therefore has the better processability energy.
Embodiment
Embodiment 1
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene and epoxy chloropropane mix; 2; 2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane are 1: 8, and said mixture heats under nitrogen protection; Heating temperature is at 90 ℃; and constantly stir, while dropping sodium solution, the concentration of used sodium hydroxide solution is 30wt%; sodium hydroxide and 2; 2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene are 2/1, and alkali lye dropwised in two hours; moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly told from system, and the epoxy chloropropane after the layering in the lower floor returns in the system.After filtration, washing removed freshen after reaction finished, and excessive epoxy chloropropane is removed in vacuum distilling (6.66KPa), and distillation temperature is no more than 150 ℃.Obtain Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.3696, adopts mphenylenediamine to solidify, condition of cure be 80 ℃ 2 hours+150 ℃ 2 hours, cured article Tg is 153.69 ℃, ultimate compression strength is 87.6MPa
Embodiment 2
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene and epoxy chloropropane mix; 2; 2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane are 1: 12, and said mixture heats under nitrogen protection; Heating temperature is at 90 ℃; and constantly stir, while dropping sodium solution, the concentration of used sodium hydroxide solution is 40wt%; sodium hydroxide and 2; 2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene are 2/1, and alkali lye dropwised in two hours; moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly told from system, and the epoxy chloropropane after the layering in the lower floor returns in the system.After filtration, washing removed freshen after reaction finished, and excessive epoxy chloropropane is removed in vacuum distilling (6.66KPa), and distillation temperature is no more than 150 ℃.Obtain Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.4212, the employing Dicyanodiamide is solidified, curing process adopts 100 parts of Resins, epoxy, 6 parts of Dicyanodiamides, 0.5 part of glyoxal ethyline, 100 ℃ solidified 2 hours earlier, solidified 4 hours at 140 ℃ then, last 170 ℃ of aftertreatments 1 hour, cured article Tg is 151.83 ℃, ultimate compression strength is 70.1MPa.
Embodiment 3
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene and epoxy chloropropane mix; 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 15; said mixture heats under nitrogen protection; Heating temperature is at 80 ℃, and constantly stirring, dropping sodium solution simultaneously; the concentration of used sodium hydroxide solution is 50wt%; sodium hydroxide and 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene is 2/1; alkali lye dropwised in two hours; after alkali lye dropwised, the temperature to 110 of rising system ℃ continued reaction 1 hour.Moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly told from system, and the epoxy chloropropane after the layering in the lower floor returns in the system.After filtration, washing removed freshen after reaction finished, and excessive epoxy chloropropane is removed in vacuum distilling (6.66KPa), and distillation temperature is no more than 150 ℃.Obtain Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.4450, adopts under the m-xylene diamine room temperature to solidify, and cured article Tg is 107.25 ℃, and ultimate compression strength is 22.0MPa.
Embodiment 4
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene; epoxy chloropropane and benzyltriethylammoinium chloride are put in the four-hole bottle together; 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 6; the benzyltriethylammoinium chloride consumption is 2; 2 '-dihydroxyl-1,1% (mol ratio) said mixture of 1 '-dinaphthalene heats under nitrogen protection, and Heating temperature is 100 ℃; reacted 2 hours; etherification reaction finishes back dropping 20wt% sodium hydroxide solution and carries out ring-closure reaction, 110 ℃ of temperature of reaction, 2 hours reaction times; after finishing after filtration; washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.4023, solidify with mphenylenediamine, condition of cure be 80 ℃ 2 hours+150 ℃ 2 hours, cured article Tg is 158.73 ℃, ultimate compression strength is 90.1MPa.
Embodiment 5
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene; epoxy chloropropane and benzyltriethylammoinium chloride are put in the four-hole bottle together; 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 8; the benzyltriethylammoinium chloride consumption is 2; 2 '-dihydroxyl-1,0.5% (mol ratio) said mixture of 1 '-dinaphthalene heats under nitrogen protection, and Heating temperature is 80 ℃; 4 hours reaction times; etherification reaction finishes back dropping 30wt% sodium hydroxide solution and carries out ring-closure reaction, 110 ℃ of temperature of reaction, 2 hours reaction times; after finishing after filtration; washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.4334, the employing Dicyanodiamide is solidified, curing process adopts 100 parts of Resins, epoxy, 6 parts of Dicyanodiamides add 0.5 part of glyoxal ethyline as promotor, and 100 ℃ solidified 2 hours earlier, solidified 4 hours at 140 ℃ then, last 170 ℃ of aftertreatments 1 hour, cured article Tg is 155.63 ℃, ultimate compression strength is 73.2MPa.
Embodiment 6
With 2; 2 '-dihydroxyl-1; 1 '-dinaphthalene; epoxy chloropropane and benzyltriethylammoinium chloride are put in the four-hole bottle together; 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 12; the benzyltriethylammoinium chloride consumption is 2; 2 '-dihydroxyl-1,1% (mol ratio) said mixture of 1 '-dinaphthalene heats under nitrogen protection, and Heating temperature is 80 ℃; 3 hours reaction times; etherification reaction finishes back dropping 40wt% sodium hydroxide solution and carries out ring-closure reaction, 110 ℃ of temperature of reaction, 3 hours reaction times; the reaction finish after after filtration; washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.The oxirane value of the Resins, epoxy of gained is 0.4528, Dicyanodiamide is solidified, curing process adopts 100 parts of Resins, epoxy, 9.5 part Dyhard RU 100,0.5 part of glyoxal ethyline, 100 ℃ solidified 2 hours earlier, solidified 4 hours at 140 ℃ then, last 170 ℃ of aftertreatments 1 hour, cured article Tg is 149.51 ℃, ultimate compression strength is 72.4MPa.
Claims (10)
1, a kind of naphthyl type Resins, epoxy, its molecular formula is:
n＝0～28。
2, the Resins, epoxy of claim 1, wherein n=0～5.
3, the Resins, epoxy of claim 2, wherein n=0～1.
4; the preparation method of the arbitrary Resins, epoxy of claim 1～3; 2; 2 '-dihydroxyl-1; the mixture of 1 '-dinaphthalene and epoxy chloropropane directly under the effect of alkali condensation obtain Resins, epoxy; concrete steps are: with 2; 2 '-dihydroxyl-1,1 '-dinaphthalene and epoxy chloropropane be by 1: 6～20 mixed in molar ratio, under protection of inert gas 80～120 ℃ of reacting by heating 2～3 hours; drip strong base solution simultaneously; highly basic and 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene is 1.04～2: 1; the reaction finish after after filtration; washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.
5, the method for claim 4, wherein highly basic is selected from sodium hydroxide, potassium hydroxide, its concentration is between 20～50wt%; Highly basic and 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene is 2: 1.
6, claim 4 or 5 method, wherein 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 6～15.
7, the preparation method of the arbitrary Resins, epoxy of claim 1～3, at first 2,2 '-dihydroxyl-1,1 '-dinaphthalene and epoxy chloropropane be etherificate under the effect of catalyzer, and closed loop obtains Resins, epoxy under the effect of alkali lye then, specifically may further comprise the steps:
(1), under protection of inert gas, 2,2 '-dihydroxyl-1, add doped quaternary ammonium salt in 1 '-dinaphthalene and the epoxy chloropropane and make catalyzer, 80～120 ℃ down heating carry out etherification reaction, wherein 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane are 1: 6～20;
(2), etherification reaction finishes back dropping strong base solution and carries out ring-closure reaction, temperature of reaction is between 100～120 ℃, by mole, the alkaline add-on is 2,2 '-dihydroxyl-1,2～2.5 times of 1 '-dinaphthalene, the reaction finish after after filtration, washing removes freshen, and excessive epoxy chloropropane is removed in vacuum distilling, obtains Resins, epoxy at last.
8, the method for claim 7, wherein in the step (1), 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene and epoxy chloropropane is 1: 6～12.
9, claim 7 or 8 method, wherein the catalyzer doped quaternary ammonium salt in the step (1) is selected from benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetraethylammonium bromide, 4 bromide.
10, claim 7 or 8 method, wherein the highly basic in the step (2) is selected from sodium hydroxide, potassium hydroxide, its concentration between 20～50wt%, highly basic and 2,2 '-dihydroxyl-1, the mol ratio of 1 '-dinaphthalene is 2: 1.
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| CN101024680B (en) * | 2007-04-05 | 2010-09-01 | 中国科学院广州化学研究所 | Binaphthyl-radicle-contained di-phenol A-type resin and its preparing method |
| WO2014073600A1 (en) * | 2012-11-08 | 2014-05-15 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, and cured product thereof |
| WO2015008560A1 (en) * | 2013-07-19 | 2015-01-22 | Dic株式会社 | Compound containing phenolic hydroxy group, photosensitive composition, composition for resists, resist coating film, curable composition, composition for resist underlayer films, and resist underlayer film |
| CN105062304A (en) * | 2015-07-22 | 2015-11-18 | 安徽圣德建材科技有限公司 | High-flame-retardant corrosion-resisting powder coating |
| CN105062303A (en) * | 2015-07-22 | 2015-11-18 | 安徽圣德建材科技有限公司 | Heat-resistant flame-retardant powder coating |
| CN111303382B (en) * | 2020-03-03 | 2020-11-10 | 深圳市勇泰运科技有限公司 | A rigid-flex integrated epoxy resin and reworkable underfill |
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