CN101906205A - Production method of non-halogen and non-phosphorus self-flame retarding epoxy resins - Google Patents
Production method of non-halogen and non-phosphorus self-flame retarding epoxy resins Download PDFInfo
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- CN101906205A CN101906205A CN 201010260020 CN201010260020A CN101906205A CN 101906205 A CN101906205 A CN 101906205A CN 201010260020 CN201010260020 CN 201010260020 CN 201010260020 A CN201010260020 A CN 201010260020A CN 101906205 A CN101906205 A CN 101906205A
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Abstract
The invention discloses a production method of non-halogen and non-phosphorus self-flame retarding epoxy resins, which is characterized in that bis-chloromethyl benzenes or aralkyl esters and organic polyphenol, according to the mole ratio of 1:(1.1-1.5), carry out condensation polymerization reaction at 80-180 DEG C in the presence of an acid catalyst to generate phenolic hydroxy resins with high content of benzene ring; and the obtained phenolic hydroxy resins is subjected to condensation and desalination with epoxy chloropropane in the presence of alkaline condition and an etherification catalyst to synthesize the epoxy resins with high functionality and high content of benzene ring. The epoxy resins produced by the method retard flame by virtue of own special structure with high content of benzene ring, do not contain halogen, dispense with addition of other organic phosphorus flame retardants and have good flame retardance. The bonding sheets and the copper clad laminates which are manufactured by the epoxy resins have high thermal resistance, high reliability, flame retardance, low water absorption rate, low coefficient of thermal expansion and good processability.
Description
Technical field
The present invention relates to a kind of production method of non-halogen and non-phosphorus self-flame retarding epoxy resins.
Background technology
Up to now, be applied in the copper-clad plate in order to produce fire-retardant Resins, epoxy, general all is the bromide fire retardant that adopts addition type, as tetrabromo-bisphenol and Resins, epoxy thereof, Poly Brominated Diphenyl Ethers etc. contain the fire retardant of bromine, particularly European Union forbids using Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers (PBDE) in electronic electric equipment, and these fire retardants are proved to be can produce carcinogenic many bromos benzo evil English (PBDD) and PBDF (PBDF) in combustion processes.Along with the growing to even greater heights of environmental protection cry, people are one after another in the alternative flame retardant products of seeking environment-friendly and green in recent years.The fire-retardant of without halide copper-clad plate mainly realized by the employing additive flame retardant, common have phosphorous, nitrogenous additive flame retardant such as phosphoric acid ester, polyphosphoric acid amine, a cyanogen urea acid trimeric cyanamide, and aluminium hydroxide, magnesium hydroxide etc., because addition is big, the performances such as glass transformation temperature (Tg), thermotolerance, processibility of sheet material are reduced; Adopt the addition type phosphonium flame retardant, also can cause the sheet material water-intake rate to rise, moisture resistance reduces, and easy layering is bubbled under the high temperature impact of sheet material when hot air leveling, components and parts assembling, and the electrical property of sheet material under wet condition also can descend.For cost, plate property and purposes are considered, it is main that additive flame retardant is still adopted in without halide paper-based copper-coated board and the compound basic copper-clad plate of without halide at present, reactive flame retardant is then mainly adopted in the copper-clad plate of without halide glass fiber fabric base, he is the Resins, epoxy benzoxazine colophony that adds nitrogenous modification in component as a kind of halogen and phosphor-free flame-proof epoxy resin composition of Chinese patent 101381506 report, nitrogenous resol, thereby play fire retardation, the composition of 101,280,093 1 kinds of Halogenless fire retarded epoxy resins of another patent disclosure, be in component, to add phosphorated Resins, epoxy, thereby play fire-retardant effect.The composition nano complexes material of 101,108,912 1 kinds of Halogenless fire retarded epoxy resins of another patent disclosure, be in component, fire retardant and polynite compound added to play in the Resins, epoxy fire-retardant effect total and right all be in component, to add to contain Phosphorus fire retardant or the nitrogen flame retardant plays fire-retardant effect.And the fire-retardant high official of the high phenyl ring special construction that relies on resin self can yet there are no too many report by Resins, epoxy.Because phosphorous waste still might endanger earth aquatic environment, therefore developing without phosphorus " three do not have " composition epoxy resin of halogen-free stibium-free, to be applied to copper-clad plate will be development in future trend.Japanese Patent reported also that the Resins, epoxy of employing bisphenol type and the phenols curing agent synthetic epoxy resin composition of aromatic ester type were used for copper-clad plate.But because this product functionality is low, phenyl ring density is not good enough, high heat resistance, high reliability, flame retardancy, low water absorption and the low thermal coefficient of expansion etc. that being difficult to reach copper-clad laminate needs have the characteristics of good processing properties and flame retardant properties.
Summary of the invention
The object of the present invention is to provide a kind of high heat resistance, high reliability, flame retardancy, low water absorption and low thermal coefficient of expansion etc. that the production method of the self-antiflaming epoxy resin of good processing properties and flame retardant properties is arranged.
The technical solution used in the present invention is as follows; A kind of production method of non-halogen and non-phosphorus self-flame retarding epoxy resins is characterized in that:
Dichloromethylation benzene class or aralkyl ethers and organic polyphenol are 1:(1.1-1.5 in molar ratio) in the presence of solid organic acid, temperature of reaction is to carry out the condensation polymerization reaction under 80-180 ℃, generates the phenol hydroxyl resin of high-content phenyl ring;
Gained phenol hydroxyl resin under catalyst for etherification, by liquid caustic soda and epoxy chloropropane condensation, desalination, the Resins, epoxy of the synthetic high phenyl ring of high functionality.
Described step
The weight-average molecular weight of middle phenol hydroxyl resin is 1000-5000,70-140 ℃ of softening temperature position, viscosity is 3000-4000cps(150 ℃).
Described step
The weight-average molecular weight of middle Resins, epoxy is 50-109 ℃ for the 880-6000 softening temperature, and viscosity is 800-2500cps(150 ℃), its epoxy equivalent (weight) is 280-450.
Described step
Middle temperature of reaction is 100-150 ℃.
Described step
In catalyst for etherification be benzyltriethylammoinium chloride.
The inventive method elder generation is by the biphenyl class of dichloromethylation, the monomer such as the 4-4-dichloride methyl biphenyl of single benzene class, to xylylene dichlorides or aralkyl ethers such as biphenyl dimethylformamide dimethyl base ether, terephthaldehyde's dimethyl ether person's mixture takes off the condensation reaction of HCL or separating methanol with phenolic monomers under the acidic catalyst effect, the HCL gas that produces in the reaction process adopts the hydrochloric acid tail gas absorption unit to carry out absorbing and removing, reaction mixture is washed 1-10 time, under normal pressure and reduced pressure thereof, dewater at last, and with unreacted free phenol, HCL gas or methyl alcohol, water is removed, form the phenol hydroxyl resin of lurid high phenyl ring at last, has high functionality, high phenyl ring density is fit to do the solidifying agent component of copper-clad plate composition epoxy resin; Then phenol hydroxyl resin under alkaline condition, catalyst for etherification by with epoxy chloropropane condensation, desalination, the Resins, epoxy of synthetic at last high functionality.
The Resins, epoxy that the inventive method is produced is fire-retardant, not halogen-containing by the high phenyl ring special construction of self, need not to add other organic phosphorus flame retardant, has excellent flame-retardant performance; With its bonding sheet of making and copper-clad laminate, have high heat resistance, high reliability, flame retardancy, low water absorption and low thermal coefficient of expansion, and have good processing properties.Flame retardant resistance reaches the UL94V-0 level, has high-peeling strength, excellent size stability, flexibility, anti-ion transport and processing characteristics.
Embodiment
Below be the embodiment that is used for a kind of non-halogen and non-phosphorus self-flame retarding epoxy resins composition of the present invention:
Embodiment 1
Under nitrogen protection; in the four-hole boiling flask that is equipped with stirrer, reflux exchanger, thermometer mouth, nitrogen mouth, HCL retrieving arrangement; the Bisphenol F of packing into 194g(1mol); water 107g, 4-4-dichloride methyl biphenyl 210g(0.85mol); heat to 80 ℃; carry out back flow reaction on one side; the HCL gas that reaction is deviate from absorbs removal through the persalt absorption unit on one side; approximately reaction is 3.5 hours; temperature of reaction slowly raises; when temperature of reaction reaches 130 ℃, keep 2 hours reaction times.The pure water that then adds about 500 grams washs, and carries out repeatedly so repeatedly, knows the directly nearly 6-7 of PH of washing back water.Under condition 140 ℃, 60mmHg, go out unreacted phenol, HCL, and a spot of water, the limit heat up backmost by the nitrogen extracting, at last when temperature reaches 150 ℃, resin imported in the stainless steel square plate cool off, obtain the about 210g of lurid solid resin, its softening temperature is made an appointment with, is 119 ℃.Again under nitrogen protection; 151g is being equipped with stirrer with the phenolic hydroxyl group resin; reflux exchanger; the thermometer mouth; in the four-hole boiling flask of nitrogen mouth; mix with the 2010g epoxy chloropropane; and adding quaternary ammonium salt catalyst; carry out etherification reaction in 70 ℃ of following heating of temperature; constantly stir; about 2.5h of reaction times; after the etherificate, while Dropwise 5 0% sodium hydroxide solution, sodium hydroxide is 1.05 with the mol ratio of phenolic hydroxyl group resin; sodium hydroxide solution dropwised in 3.5 hours; moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly separated from system, and through phase splitter, epoxy chloropropane constantly returns in the system.After reaction finishes after filtration, wash, go out the salt that generates, vacuum distilling, under reduced pressure, remove excessive epoxy chloropropane, under the alkali lye condition that adds MIBK and a small amount of 5%, under 95 ℃ of conditions, stir refining 2h, the organochlorine of trace is deviate from washing at last, desolventizing at last reduces pressure, obtain the self-antiflaming epoxy resin that lurid solid resin is the high phenyl ring of high functionality, 85 ℃ of softening temperatures, 150 ℃ of viscosity 2000cps.
Embodiment 2
Under nitrogen protection; in the four-hole boiling flask that is equipped with stirrer, reflux exchanger, thermometer mouth, nitrogen mouth device; phenol 94g(1mol packs into), water 107g, biphenyl dimethylformamide dimethyl base ether 205g(0.82mol), heat to 80 ℃; carry out back flow reaction on one side; the methanol gas that reaction is deviate from absorbs through condenser condenses and removes on one side, approximately reacts 3.5 hours, and temperature of reaction slowly raises; when temperature of reaction reaches 130 ℃, keep 2 hours reaction times.The pure water that then adds about 500 grams washs, and carries out repeatedly so repeatedly, knows the directly nearly 6-7 of PH of washing back water.Under condition 140 ℃, 60mmHg, go out unreacted small molecules phenol, HCL, and a spot of water, the limit heat up backmost by the nitrogen extracting, at last when temperature reaches 150 ℃, resin imported in the stainless steel square plate cool off, obtain the about 305g of lurid solid resin, its softening temperature is 114 ℃.Again under nitrogen protection; 173g is being equipped with stirrer with the phenolic hydroxyl group resin; reflux exchanger; the thermometer mouth; in the four-hole boiling flask of nitrogen mouth; mix with the 1910g epoxy chloropropane; and adding quaternary ammonium salt catalyst; carry out etherification reaction in 70 ℃ of following heating of temperature; constantly stir; about 2.5h of reaction times; after the etherificate, while Dropwise 5 0% sodium hydroxide solution, sodium hydroxide is 1.06 with the mol ratio of phenolic hydroxyl group resin; sodium hydroxide solution dropwised in 3.5 hours; moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly separated from system, and through phase splitter, epoxy chloropropane constantly returns in the system.After reaction finishes after filtration, wash, go out the salt that generates, vacuum distilling, under reduced pressure, remove excessive epoxy chloropropane, under the alkali lye condition that adds MIBK and a small amount of 5%, under 95 ℃ of conditions, stir refining 2h, the organochlorine of trace is deviate from washing at last, desolventizing at last reduces pressure, obtain the Resins, epoxy that lurid solid resin is the high phenyl ring of high functionality, 75 ℃ of softening temperatures, 150 ℃ of viscosity 1020cps.
Embodiment 3
Under nitrogen protection; in the four-hole boiling flask that is equipped with stirrer, reflux exchanger, thermometer mouth, nitrogen mouth device; the Bisphenol F of packing into 194g(1mol), water 107g, biphenyl dimethylformamide dimethyl base ether 232g(0.93mol), heat to 80 ℃; carry out back flow reaction on one side; the methanol gas that reaction is deviate from reclaims through condenser condenses on one side, approximately reacts 3.5 hours, and temperature of reaction slowly raises; when temperature of reaction reaches 130 ℃, keep 2 hours reaction times.The pure water that then adds about 500 grams washs, and carries out repeatedly so repeatedly, until the directly nearly 6-7 of the PH of washing back water.Under condition 140 ℃, 60mmHg, distill out unreacted phenol, HCL, reach a spot of water, the limit heat up backmost by the nitrogen extracting, at last when temperature reaches 150 ℃, resin imported in the stainless steel square plate cool off, obtain the about 318g of lurid solid resin, its softening temperature is 130 ℃, 150 ℃ of viscosity 3870cps; Again under nitrogen protection; 151g is being equipped with stirrer with the phenolic hydroxyl group resin; reflux exchanger; the thermometer mouth; in the four-hole boiling flask of nitrogen mouth; mix with the 2010g epoxy chloropropane; and adding quaternary ammonium salt catalyst; carry out etherification reaction in 70 ℃ of following heating of temperature; constantly stir; about 2.5h of reaction times; after the etherificate, while Dropwise 5 0% sodium hydroxide solution, sodium hydroxide is 1.05 with the mol ratio of phenolic hydroxyl group resin; sodium hydroxide solution dropwised in 3.5 hours; moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly separated from system, and through phase splitter, epoxy chloropropane constantly returns in the system.After reaction finishes after filtration, wash, go out the salt that generates, vacuum distilling, under reduced pressure, remove excessive epoxy chloropropane, under the alkali lye condition that adds MIBK and a small amount of 5%, under 95 ℃ of conditions, stir refining 2h, the organochlorine of trace is deviate from washing at last, desolventizing at last reduces pressure, obtain the Resins, epoxy that lurid solid resin is the high phenyl ring of high functionality, 85 ℃ of softening temperatures, 150 ℃ of viscosity 2000cps.
Embodiment 4
Under nitrogen protection; in the four-hole boiling flask that is equipped with stirrer, reflux exchanger, thermometer mouth, nitrogen mouth, HCL retrieving arrangement; phenol 94g(1mol packs into), water 107g, biphenyl dimethylformamide dimethyl base ether 198g(0.82mol), heat to 80 ℃; carry out back flow reaction on one side; the methanol gas that reaction is deviate from absorbs through condenser condenses and removes on one side, approximately reacts 3.5 hours, and temperature of reaction slowly raises; when temperature of reaction reaches 130 ℃, keep 2 hours reaction times.The pure water that then adds about 500 grams washs, and carries out repeatedly so repeatedly, knows the directly nearly 6-7 of PH of washing back water.Under condition 140 ℃, 60mmHg, go out unreacted small molecules phenol, HCL, and a spot of water, the limit heat up backmost by the nitrogen extracting, at last when temperature reaches 150 ℃, resin imported in the stainless steel square plate cool off, obtain the about 305g of lurid solid resin, its softening temperature is 111 ℃; Again under nitrogen protection; with phenolic hydroxyl group resin 202g; stirrer is being equipped with; reflux exchanger; the thermometer mouth; in the four-hole boiling flask of nitrogen mouth; mix with the 2300g epoxy chloropropane; and adding quaternary ammonium salt catalyst; carry out etherification reaction in 70 ℃ of following heating of temperature; constantly stir, about 2.5h of reaction times is after the etherificate; while Dropwise 5 0% sodium hydroxide solution; sodium hydroxide is 1.05 with the mol ratio of phenolic hydroxyl group resin, and sodium hydroxide solution dropwised in 3.5 hours, and moisture in reaction process in the system and epoxy chloropropane azeotropic are constantly separated from system; through phase splitter, epoxy chloropropane constantly returns in the system.After reaction finishes after filtration, wash, go out the salt that generates, vacuum distilling, under reduced pressure, remove excessive epoxy chloropropane, under the alkali lye condition that adds MIBK and a small amount of 5%, under 95 ℃ of conditions, stir refining 2h, the organochlorine of trace is deviate from washing at last, desolventizing at last reduces pressure, obtain the Resins, epoxy that lurid solid resin is the high phenyl ring of high functionality, 68 ℃ of softening temperatures, 150 ℃ of viscosity 870cps.
Claims (6)
1. the production method of a non-halogen and non-phosphorus self-flame retarding epoxy resins is characterized in that:
Dichloromethylation benzene class or aralkyl ethers and organic polyphenol are 1:(1.1-1.5 in molar ratio) in the presence of solid organic acid, temperature of reaction is to carry out the condensation polymerization reaction under 80-180 ℃, generates the phenol hydroxyl resin of high-content phenyl ring;
Gained phenol hydroxyl resin by condensation reaction, the desalination of epoxy chloropropane and liquid caustic soda, synthesizes the Resins, epoxy of the high phenyl ring of high functionality under catalyst for etherification.
2. production method according to claim 1 is characterized in that: described step
The weight-average molecular weight of middle phenol hydroxyl resin is 1000-5000,70-140 ℃ of softening temperature position, viscosity is 3000-4000cps(150 ℃).
3. production method according to claim 1 is characterized in that: described step
The weight-average molecular weight of middle Resins, epoxy is 50-109 ℃ for the 880-6000 softening temperature, and viscosity is 800-2500cps(150 ℃), its epoxy equivalent (weight) is 280-450.
4. production method according to claim 1 is characterized in that: described step
Middle temperature of reaction is 100-150 ℃.
5. production method according to claim 1 is characterized in that: described step
In catalyst for etherification be benzyltriethylammoinium chloride.
6. production method according to claim 1 is characterized in that: described solid organic acid is oxalic acid, p-methyl benzenesulfonic acid, organic phosphoric acid, sulfuric acid, hydrochloric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010260020 CN101906205A (en) | 2010-08-23 | 2010-08-23 | Production method of non-halogen and non-phosphorus self-flame retarding epoxy resins |
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| CN 201010260020 CN101906205A (en) | 2010-08-23 | 2010-08-23 | Production method of non-halogen and non-phosphorus self-flame retarding epoxy resins |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928432A (en) * | 2017-04-24 | 2017-07-07 | 湖南嘉盛德材料科技有限公司 | A kind of intrinsic fire retarding epoxide resin of Halogen and its synthetic method |
| WO2023276851A1 (en) * | 2021-06-30 | 2023-01-05 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, epoxy resin composition, and cured product of same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255603A (en) * | 1996-03-26 | 1997-09-30 | Meiwa Kasei Kk | Bis(hidroxybenzyl)biphenyl and its production |
| CN1174851A (en) * | 1996-08-23 | 1998-03-04 | 日本化药株式会社 | Modified epoxy resin, epoxy resin composition and cured product thereof |
| JP2007063339A (en) * | 2005-08-30 | 2007-03-15 | Sumitomo Bakelite Co Ltd | Biphenylaralkyl-modified phenolic resin and method for producing the same, epoxy resin molding material containing the same |
-
2010
- 2010-08-23 CN CN 201010260020 patent/CN101906205A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255603A (en) * | 1996-03-26 | 1997-09-30 | Meiwa Kasei Kk | Bis(hidroxybenzyl)biphenyl and its production |
| CN1174851A (en) * | 1996-08-23 | 1998-03-04 | 日本化药株式会社 | Modified epoxy resin, epoxy resin composition and cured product thereof |
| JP2007063339A (en) * | 2005-08-30 | 2007-03-15 | Sumitomo Bakelite Co Ltd | Biphenylaralkyl-modified phenolic resin and method for producing the same, epoxy resin molding material containing the same |
Non-Patent Citations (1)
| Title |
|---|
| 《化工新型材料》 20081130 谭怀山 新型含联苯结构环氧树脂的合成与性能 第49-50，61页 1-6 第36卷, 第11期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928432A (en) * | 2017-04-24 | 2017-07-07 | 湖南嘉盛德材料科技有限公司 | A kind of intrinsic fire retarding epoxide resin of Halogen and its synthetic method |
| WO2023276851A1 (en) * | 2021-06-30 | 2023-01-05 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, epoxy resin composition, and cured product of same |
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Open date: 20101208 |