CN101070372A - Resin-modified method epoxy resin and preparing method - Google Patents
Resin-modified method epoxy resin and preparing method Download PDFInfo
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- CN101070372A CN101070372A CN 200610166850 CN200610166850A CN101070372A CN 101070372 A CN101070372 A CN 101070372A CN 200610166850 CN200610166850 CN 200610166850 CN 200610166850 A CN200610166850 A CN 200610166850A CN 101070372 A CN101070372 A CN 101070372A
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Abstract
The present invention relates to a kind of epoxy-phenolic resin modified by rosin and its preparation method. The said epoxy-phenolic resin has the above structure, in which R represents H or nonyl, n=1,2...10. The preparation method, firstly, melts resin, and feeds phenol or nonylphenol, formaldehyde and ZnO or MgO catalyst under the protection of nitrogen, then after refluxing for some time, warms and vacuum dehydrates to obtain the epoxy-phenolic resin modified by rosin; feeds epichlorohydrin and catalysts, after reacting for some time, vacuum distillates and feeds organic solvents to dissolve; drops alkali solution used in closed-loop or slowly feeds solid bases or metal oxides both fine grinded, after reacting for some time, washes to neutral by water, then distillates and recovers the solution to obtain brown transparent epoxy resin products. After solidifying, the products have better heat resistance and electrical insulation property, and are applied to electronic packaging, coatings, etc.
Description
Technical field
The present invention relates to a kind of Abietyl modified novolac epoxy and preparation method thereof, belong to chemical field.
Technical background
Resins, epoxy (epoxy resin) is a kind of oligopolymer with epoxy group(ing), just can form the thermosetting resin with tridimensional network after reacting with solidifying agent.The kind of Resins, epoxy is a lot, can roughly be divided into Racemic glycidol ethers, glycidyl ester class, Racemic glycidol amine, the alicyclic ring same clan, line style aliphatic category according to chemical structure.
The method of synthetic epoxy resin has multiple, and roughly can be divided into according to the method difference of introducing epoxy group(ing) in molecule: the compound and epichlorohydrin reaction, double bond containing compound and peroxide reactions, the double bond containing compound that contain reactive hydrogen react through superoxide.But it is that nothing is appointed for which kind of method, reduces fragility, and improving thermotolerance is the emphasis of this area researchist work all the time.Because there is the relatively poor shortcoming of thermotolerance in pure epoxy resin, be subjected to many restrictions in actual applications, many for this reason scientific research personnel wish to improve its thermotolerance as far as possible, to adapt to the better application of Resins, epoxy in fields such as Electronic Packaging, printing ink by the whole bag of tricks.
According to the relation principle of macromolecular structure and performance, improve stable on heating main path and be the preparation multiple functionality epoxide resin, in resin, introduce rigid structure, improve curing cross-linked density, and select number of ways such as thermotolerance solidifying agent for use.
In order to give substrate ring epoxy resins better heat-resisting, have a lot of methods that disclose so far, in the Resins, epoxy molecular structure, introduce inflexible polynuclear aromatic family's group such as naphthyl etc. as passing through, thereby improve the thermotolerance of cured resin.In Chinese invention patent specification sheets (the ZL patent No. 00801694.1), a kind of aromatics and unsaturated cyclic hydrocarbon compound method of preparing thermotolerance and coloury, as to can be used for semiconductor-encapsulating material and laminate sheet material resol and Resins, epoxy under the acid catalyst effect with hydroxyl proposed, wherein only the hydroxyl aromatics for example in mentioned 1-naphthols and beta naphthal, do not provide specific description, also do not relate to the reaction of they and aldehyde and ketone.U.S. Pat Pat5,068,293 and publication number CN1160724 disclose respectively a kind of by the naphthols or derivatives thereof with produce the polyfunctional epoxy resin that condensation reaction makes to two through methylbenzene with to xylenediol, but these " bridge " half polycondensation monomer costliness and commercial being difficult to of connecting naphthols obtain, Tg is also not very too high behind the epoxy resin cure of gained, usually less than 170 ℃.U.S. Pat Pat 4,687,832 disclose a kind of by dihydroxy naphthlene with the propylene oxide etherificate and must Resins, epoxy also have similar problem, raw materials cost is higher, yield is lower during etherificate.Because its glycidyl ether functional group density is big, the water-intake rate of cured article is also bigger.Chinese patent polyfunctional epoxy resin and preparation method thereof (ZL 02135023.X) discloses a kind of polyfunctional epoxy resin and preparation method thereof.Though this method has some improvement at aspects such as product properties, preparation process must be used alkaline catalysts, and range of choice is less, and the process more complicated.
Resins, epoxy performance at high temperature depends primarily on its heat-drawn wire and thermo-oxidative stability.The functional group of Resins, epoxy own is many more, and distance is more little between two epoxy group(ing), and resin crosslinks density is big more after solidifying, and heat-drawn wire is high more, and thermotolerance is good more.Thereby improving the Resins, epoxy functionality is one of approach that improves its resistance toheat, as epoxidation phenolic aldehyde, bisphenol S epoxy, amino four sense epoxies, chloro four sense epoxies better heat-resisting is arranged all.
In resin, introduce rigid polymer and equally also can improve thermotolerance and work, but will solve the compatibility problem of rigid polymer and Resins, epoxy Resins, epoxy.
Cycloaliphatic epoxy resin also has good thermotolerance.Cycloaliphatic epoxy resin is a raw material with the alicyclic compound of band ethylene linkage normally, makes through epoxidation reaction.Because the epoxy group(ing) in the cycloaliphatic epoxy resin molecular structure is not from propylene oxide, but epoxy group(ing) directly is connected on the alicyclic ring, so cycloaliphatic epoxy resin has good thermal stability, and the advantage of good weatherability.
Because Si-O key bond energy height, thereby organosilyl Heat stability is good.With organosilicon Resins, epoxy is carried out modification, also can improve the thermotolerance of Resins, epoxy.But the solubility parameter of the two differs bigger, and consistency is poor.If can improve the consistency of organosilicon and Resins, epoxy, just can obtain having the Resins, epoxy of good heat resistance energy.
If on the main chain of Resins, epoxy or side chain, introduce siloxane bond, also can improve the thermotolerance of Resins, epoxy.The use of high temperature resistant solidifying agent also is a good approach that improves the epoxy resin cured product resistance toheat.
Purpose of the present invention will provide a kind of ehter bond that 1. contains exactly, can give Resins, epoxy and have excellent electric insulation performance and good resistance to chemical reagents; 2. having a plurality ofly can provide reactive oxirane ring, and it is big to solidify back resin crosslinks density, the Resins, epoxy of chemical resistance and good heat resistance.
Summary of the invention
For realizing that the technical scheme that purpose of the present invention adopts is: utilize abundant rosin resource, resol is carried out modification, and then prepare a kind of novolac epoxy of gathering ethoxylated glycerol type and glyceryl ester type.
Resins, epoxy provided by the invention has following chemical structure:
Wherein R is H or nonyl, n=1,2 ... 10.
Concrete preparation method is as follows:
1, earlier the rosin of 100 weight parts is pulverized, is heated to 140 ℃ and make it fusing; feeding nitrogen protects; the ZnO or the MgO that add nonyl phenol, 17 parts by weight of formaldehyde and 0.2～0.6 weight part of 16 weight part phenol or 37 weight parts simultaneously; at 90～110 ℃ of 3～5h that reflux; continue to be warming up to 180～210 ℃ then; and behind 180～210 ℃ of vacuum hydro-extraction 1h, lower the temperature, obtain rosin modified phenolic resin.
2, in rosin modified phenolic resin, add 50～120 weight part epoxy chloropropane and 2～7 weight part catalyzer, after reacting 1～3h between 60～130 ℃, carry out underpressure distillation, and add 100 weight part organic solvents and dissolve.
3, between 25～70 ℃, drip concentration while stirring and be 10%～30% alkali solution used in closed-loop or slowly add and be ground to fine grain solid alkali, or metal oxide, the amount of adding is 4.3～43 weight parts, keeps temperature to continue reaction 1～7h.
4, after reaction finished, product was washed with water to neutrality, and distillating recovering solvent obtains brown transparent Resins, epoxy product.
Catalyzer described in the present invention is meant tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyl ammonium chloride, benzyl brometo de amonio or sodium hydroxide, potassium hydroxide or magnesium oxide, zinc oxide.
Alkali described in the preparation method of the present invention (3) is meant solid sodium hydroxide, solid potassium hydroxide or its solution, or solid oxidation magnesium, solid oxidation zinc basic oxide.
Organic solvent of the present invention is meant benzene,toluene,xylene.
Rosin of the present invention is gum resin, wood rosin, starex or rosiny main component resinous acid.The Abietyl modified novolac epoxy that the present invention prepares can with polyamides ammonium, Tetra hydro Phthalic anhydride or 4, the 4-diaminodiphenylsulfone(DDS) solidifies, the cured product that obtains has good thermotolerance and excellent electrical insulation capability and resistance to chemical corrosion.
The oxirane value of the Abietyl modified novolac epoxy that the present invention prepares is 0.2～0.4mol/100g.The innovation part of this invention is: with renewable resources---rosin is raw material, and resol is carried out modification, and then synthesizes a kind of novel Resins, epoxy, obtains new class rosin deep processed product, to improve the rosiny added value.
A. the synthetic Resins, epoxy kind that obtains the new fine heat-resisting performance of a class.
B. the synthetic neo-epoxy resin has excellent electric insulation performance and resistance to chemical reagents.
C. invent a kind of synthetic method, making the synthetic Abietyl modified novolac epoxy that obtains is the neo-epoxy resin of set glycidyl ether type and glycidyl ester type.
D. the Abietyl modified novolac epoxy that adopts the present invention to make has good thermotolerance, and good chemical resistance, can be used for the field such as encapsulation, casting, anticorrosive coating, thermotolerance coating of electronic devices and components.
Embodiment
Following specific embodiment is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1
Earlier gum resin 100g is pulverized and be heated to 140 ℃ and make it fusing, flow velocity with per second 2mL feeds nitrogen, add the MgO catalyzer of 16g phenol, 17g formaldehyde and 0.6g, backflow 5h in the time of 95 ℃ continues to be warming up to the vacuum hydro-extraction of carrying out 1h after 180 ℃ then and promptly obtains rosin modified phenolic resin.
Add 100g epoxy chloropropane and 2g tetramethyl ammonium chloride after rosin modified phenolic resin is cooled to 70 ℃, keep thermotonus 3h after, excessive epoxy chloropropane is reclaimed in the reaction solution underpressure distillation, and the benzole soln of adding 100g.
It is 10% NaOH solution 10g that reaction system drips concentration while stirring in 40 ℃, keeps thermotonus 6h.
After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Embodiment 2
Earlier wood rosin 100g is pulverized and be heated to 140 ℃ and make it fusing; flow velocity with per second 2mL feeds nitrogen protection; the ZnO catalyst that adds nonyl phenol, 17g formaldehyde and the 0.5g of 37g; backflow 3h in the time of 110 ℃ continues to be warming up to the rosin modified phenolic resin that the vacuum hydro-extraction of carrying out 1h after 200 ℃ promptly obtains then.
Add the 120g epoxy chloropropane after rosin modified phenolic resin is cooled to 100 ℃ and be ground to fine grain solid sodium hydroxide, its consumption is 4g, behind the maintenance thermotonus 2h, and the reaction solution underpressure distillation, reclaim excessive epoxy chloropropane, and add the solvent toluene of 100g.
It is 20% KOH solution 15g that system drips concentration while stirring in 65 ℃, keeps thermotonus 4h.After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Embodiment 3
Earlier starex 100g is pulverized and be heated to 140 ℃ and make it fusing, flow velocity with per second 2mL feeds nitrogen, add the MgO of 16g phenol, 17g formaldehyde and 0.2g, backflow 4h in the time of 90 ℃ continues to be warming up to the vacuum hydro-extraction of carrying out 1h after 210 ℃ then and promptly obtains rosin modified phenolic resin.
Add 60g epoxy chloropropane and NaOH solution after rosin modified phenolic resin is cooled to 60 ℃, its consumption is 6g, keep thermotonus 3h after, carry out underpressure distillation, reclaims excessive epoxy chloropropane, and the solvent xylene of adding 100g.
System slowly adds while stirring in 25 ℃ and is ground to fine grain solid NaOH, and consumption is 25g, keeps thermotonus 4h.
After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Embodiment 4
Earlier wood rosin 100g is pulverized and be heated to 140 ℃ and make it fusing, flow velocity with per second 2mL feeds nitrogen, add the ZnO of nonyl phenol, 17g formaldehyde and the 0.4g of 37g, backflow 3h in the time of 100 ℃ continues to be warming up to the vacuum hydro-extraction of carrying out 1h after 180 ℃ then and promptly obtains rosin modified phenolic resin.
Rosin modified phenolic resin is cooled to 130 ℃ to add the 100g epoxy chloropropane and is ground to fine grain solid oxidation zinc catalyst, catalyst levels is 7g, behind the maintenance thermotonus 3h, and the reaction solution underpressure distillation, reclaim excessive epoxy chloropropane, and add the solvent benzol of 100g.
System slowly adds while stirring in 45 ℃ and is ground to fine grain solid oxidation zinc, and consumption is 30g, keeps thermotonus 6h.
After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Embodiment 5
Earlier gum resin 100g is pulverized and be heated to 140 ℃ and make it fusing, flow velocity with per second 2mL feeds nitrogen, the MgO that adds 16g phenol, 17g formaldehyde and 0.04g, backflow 3h in the time of 100 ℃ continues to be warming up to 180 ℃ then and carries out 1h vacuum hydro-extraction and promptly obtain rosin modified phenolic resin.
Rosin modified phenolic resin is cooled to 130 ℃ adds 100g epoxy chloropropane and etamon chloride catalyzer, catalyst levels is 7g, and behind the maintenance thermotonus 3h, excessive epoxy chloropropane is reclaimed in the reaction solution underpressure distillation, and adds the solvent benzol of 100g.
System slowly adds while stirring in about 45 ℃ and is ground to fine grain solid MgO, and consumption is 43g, keeps thermotonus 4h.
After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Embodiment 6
Earlier resinous acid 100g is pulverized and be heated to 140 ℃ and make it fusing, flow velocity with per second 2mL feeds nitrogen, add 37g nonyl phenol, 17g formaldehyde and 0.5g ZnO, backflow 3h in the time of 100 ℃ continues to be warming up to 180 ℃ then and carries out 1h vacuum hydro-extraction and promptly obtain rosin modified phenolic resin.
Rosin modified phenolic resin is cooled to 100 ℃ adds 100g epoxy chloropropane and benzyl ammonium chloride catalyzer, catalyst levels is 6g, and behind the maintenance thermotonus 3h, excessive epoxy chloropropane is reclaimed in the reaction solution underpressure distillation, and adds excessive solvent benzol.
System fully stirs in 50 ℃, and to begin to drip concentration be 30% NaOH solution, and the amount of dropping is 40g, keeps thermotonus 5h.
After reaction finished, product was washed with water to neutrality, and vacuum distillation recovered solvent obtains brown transparent Resins, epoxy product.
Claims (6)
1, a kind of Abietyl modified novolac epoxy has following structure:
Wherein R is H or nonyl, n=1,2 ... 10.
2, a kind of preparation method of Abietyl modified novolac epoxy is characterized in that:
The rosin of (1) 100 weight part pulverizes, heat fused, feed nitrogen, the nonyl phenol, 17～20 parts by weight of formaldehyde, 0.2～0.6 weight part ZnO or the MgO that add 16～18 weight part phenol or 37～40 weight parts are at 90～110 ℃ of 3～5h that reflux, at 180～210 ℃ of vacuum hydro-extraction 1h.
(2) add 50～120 weight part epoxy chloropropane and 2～7 weight part catalyzer, after reacting 1～3h between 60～130 ℃, carry out underpressure distillation, and add 100 weight part organic solvents.
(3) between 25～70 ℃, dropping concentration is 10%～30% alkaline solution or adds solid alkali or metal oxide that the amount of adding is 4.3～43 weight parts, continues reaction 1～7h.
(4) washing is to neutral, and distillating recovering solvent obtains the Resins, epoxy product.
3, the preparation method of Abietyl modified novolac epoxy according to claim 2 is characterized in that described rosin is gum resin, wood rosin, starex or rosiny main component resinous acid.
4, the preparation method of Abietyl modified novolac epoxy according to claim 2 is characterized in that described catalyzer is tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyl ammonium chloride, benzyl brometo de amonio or sodium hydroxide, potassium hydroxide or magnesium oxide, zinc oxide.
5, the preparation method of Abietyl modified novolac epoxy according to claim 2 is characterized in that described alkali is solid sodium hydroxide, solid potassium hydroxide or its solution.
6, the preparation method of Abietyl modified novolac epoxy according to claim 2 is characterized in that described metal oxide is magnesium oxide, zinc oxide.
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| CNB2006101668504A CN100526359C (en) | 2006-12-05 | 2006-12-05 | Resin-modified method epoxy resin and preparing method |
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| CN101899196A (en) * | 2010-07-29 | 2010-12-01 | 华南理工大学 | Water-borne phenolic epoxy resin emulsion and preparation method thereof |
| CN102206318A (en) * | 2010-03-31 | 2011-10-05 | 新洲(武平)林化有限公司 | New process for preparing rosin modified phenolic resin |
| CN102532446A (en) * | 2011-12-21 | 2012-07-04 | 桂林兴松林化有限责任公司 | Preparation method of mixed phenolic rosin modified phenolic resin |
| CN102993897A (en) * | 2012-11-26 | 2013-03-27 | 安徽西格尔涂料科技有限公司 | Preparation method of silica-modified resin for waterborne insulating paint |
| CN102993395A (en) * | 2012-11-26 | 2013-03-27 | 安徽西格尔涂料科技有限公司 | Method for preparing resin for water-based insulating varnish |
| CN104693391A (en) * | 2015-03-23 | 2015-06-10 | 武汉工程大学 | Epoxy phenolic resin and synthetic method thereof |
| CN106279588A (en) * | 2016-08-29 | 2017-01-04 | 广西梧州通轩林产化学有限公司 | The preparation method of coating rosin modified phenolic resin |
| CN107216806A (en) * | 2017-07-20 | 2017-09-29 | 苏州文仓乐器有限公司 | A kind of metal handicrafts insulated paint |
| CN112442157A (en) * | 2019-09-05 | 2021-03-05 | 彤程化学（中国）有限公司 | Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof |
| CN114574104A (en) * | 2022-03-18 | 2022-06-03 | 广西科茂林化有限公司 | Ultraviolet light cured rosin resin and preparation method and application thereof |
| CN114907742A (en) * | 2022-05-17 | 2022-08-16 | 广州胜帆新材料科技有限公司 | Mildew-proof antibacterial anti-rubbing interior wall coating |
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| JP3893423B2 (en) * | 1999-08-13 | 2007-03-14 | 新日本石油株式会社 | Method for producing phenolic resin and epoxy resin |
| CN1179996C (en) * | 2002-10-25 | 2004-12-15 | 中国科学院广州化学研究所 | Polyfunctional epoxy resin and its preparation method |
| CN100500761C (en) * | 2005-12-20 | 2009-06-17 | 东莞理工学院 | Composition of non-halogen flame retarded type epoxy resin and semi-solidified sheet containing same composition and copper foil clad laminated board |
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| CN102206318A (en) * | 2010-03-31 | 2011-10-05 | 新洲(武平)林化有限公司 | New process for preparing rosin modified phenolic resin |
| CN101899196A (en) * | 2010-07-29 | 2010-12-01 | 华南理工大学 | Water-borne phenolic epoxy resin emulsion and preparation method thereof |
| CN101899196B (en) * | 2010-07-29 | 2012-10-31 | 华南理工大学 | Water-borne phenolic epoxy resin emulsion and preparation method thereof |
| CN102532446A (en) * | 2011-12-21 | 2012-07-04 | 桂林兴松林化有限责任公司 | Preparation method of mixed phenolic rosin modified phenolic resin |
| CN102993897A (en) * | 2012-11-26 | 2013-03-27 | 安徽西格尔涂料科技有限公司 | Preparation method of silica-modified resin for waterborne insulating paint |
| CN102993395A (en) * | 2012-11-26 | 2013-03-27 | 安徽西格尔涂料科技有限公司 | Method for preparing resin for water-based insulating varnish |
| CN104693391A (en) * | 2015-03-23 | 2015-06-10 | 武汉工程大学 | Epoxy phenolic resin and synthetic method thereof |
| CN106279588A (en) * | 2016-08-29 | 2017-01-04 | 广西梧州通轩林产化学有限公司 | The preparation method of coating rosin modified phenolic resin |
| CN107216806A (en) * | 2017-07-20 | 2017-09-29 | 苏州文仓乐器有限公司 | A kind of metal handicrafts insulated paint |
| CN112442157A (en) * | 2019-09-05 | 2021-03-05 | 彤程化学（中国）有限公司 | Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof |
| CN114574104A (en) * | 2022-03-18 | 2022-06-03 | 广西科茂林化有限公司 | Ultraviolet light cured rosin resin and preparation method and application thereof |
| NL2031958B1 (en) | 2022-03-18 | 2022-12-13 | Guangxi Komo Co Ltd | An ultraviolet light curable rosin resin, preparation method and application thereof |
| CN114574104B (en) * | 2022-03-18 | 2023-12-19 | 广西科茂林化有限公司 | Ultraviolet light cured rosin resin and preparation method and application thereof |
| CN114907742A (en) * | 2022-05-17 | 2022-08-16 | 广州胜帆新材料科技有限公司 | Mildew-proof antibacterial anti-rubbing interior wall coating |
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