CN103254381A - Preparation method of nitrogenous phenolic resin in one-step synthesis process - Google Patents
Preparation method of nitrogenous phenolic resin in one-step synthesis process Download PDFInfo
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- CN103254381A CN103254381A CN201310184439XA CN201310184439A CN103254381A CN 103254381 A CN103254381 A CN 103254381A CN 201310184439X A CN201310184439X A CN 201310184439XA CN 201310184439 A CN201310184439 A CN 201310184439A CN 103254381 A CN103254381 A CN 103254381A
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Abstract
The invention relates to a preparation method of a nitrogenous phenolic resin in a one-step synthesis process, and belongs to the technical field of environment-friendly flame retardants. The method comprises the following steps of: under a catalysis condition of an alkali catalyst of which a pH value is 8-10, preparing a nitrogenous phenolic resin solution by using phenol or para-position and ortho-position substituted alkylphenol, methanol and guanidine amine monomers through a one-step copolycondensation process; simultaneously adding a copolycondensation monomer reaction rate regulating agent and a solvent for performing copolycondensation reaction for 2-5 hours at 80-100 DEG C under constant pressure; and missing a dehydration step and directly obtaining the homogeneous nitrogenous phenolic resin solution with stable storage. The preparation method has the advantages of simple preparation method and easiness for industrial production; the nitrogenous phenolic resin solution can be directly prepared; and the prepared nitrogenous phenolic resin solution, epoxy resins, phosphorus-containing epoxy resins and benzoxazine resins are high in compatibility; and because of positive-negative (P-N) synergistic effect formed in a system, the ideal flame retardant effect can be realized, and the using amount of the phosphorus-containing epoxy resins is effectively reduced.
Description
Technical field
The present invention relates to nitrogenous resol preparation method, the nitrogenous resol preparation method of especially a kind of one-step synthesis belongs to the environmental protection fire retarding agent technical field.
Background technology
Understand according to the applicant, at present FR-4 copper-clad plate halogen-free flameproof mainstream technology is: be resin matrix with phosphorous epoxy resin, o-cresol formaldehyde epoxy resin etc., be solidifying agent with nitrogenous resol, be auxiliary solidifying agent with Dyhard RU 100, imidazoles etc., add inorganic combustion inhibitors such as a certain amount of aluminium hydroxide and magnesium hydroxide, through the dipping, dry prepreg, will obtain non-halogen fire-retardant FR-4 copper-clad plate behind the repressed curing molding of prepreg again.
Phosphorous epoxy resin mainly is to be main fire retardant with DOPO, and be that matrix resin is (as phenol novolac epoxy resins with itself and multifunctional heat-resisting novolac epoxy, o-cresol formaldehyde epoxy resin etc.), or carrying out addition polymerization with the dihydroxyphenyl propane tetraglycidel ether epoxy resin, the phosphorus content of preparation is 3 ± 0.5% and the phosphorous epoxy resin of oxirane value 0.3 ± 0.3.Using the main purpose of o-cresol formaldehyde epoxy resin is to have a higher second-order transition temperature in order to adjust the resin matrix system.Using nitrogenous resol purpose is to make the resin matrix system easily form the P-N synergistic effect, with the Resins, epoxy of lower phosphorus content, can reach desirable flame retardant effect equally like this.As the halogen-free flameproof mainstream technology, phosphorous epoxy resin/nitrogenous phenolic resin as matrix resin system has satisfied the demand of FR-4 copper-clad plate halogen-free flameproof basically.
In above-mentioned resin matrix system, nitrogenous resol is the good solidifying agent of phosphorous epoxy resin, it is again a kind of nitrogen based flame retardant, it and phosphorus play the cooperative flame retardant effect, introduce nitrogenous resol to the resin matrix system and can not lose some good characteristic (as specific inductivity, cross-linking density, cohesiveness etc.).Because the adding of nitrogenous resol has been brought into play the P-N flame retardant synergistic effect, thereby has been reduced the phosphorous consumption of resin matrix system, with thermotolerance, water tolerance and the chemical proofing that improves whole resin system cured article.This nitrogenous resol has following characteristics: belong to the nitrogen flame retardant, toxicity is less, flame retarding efficiency is high, corrodibility is little, heat decomposition temperature is high; This has also determined nitrogenous resol to play important effect in the future in the flow of research of environmentally friendly copper-clad plate.
Nitrogenous resol is all synthetic through two-step approach under the basic catalyst catalytic condition by trimeric cyanamide, phenol and formaldehyde usually, namely adopting phenol or contraposition and ortho position alkyl-substituted phenols is that monomer and formaldehyde, trimeric cyanamide or guanamines class monomer are synthetic under the basic catalyst catalytic condition of 8-10 in the pH value.At first prepare many melamine methylols, be added drop-wise to then that the two-stage process that carries out copolycondensation in the phenol formaldehyde (PF) prepolymer again prepares.The shortcoming of this method is that the stability of many melamine methylols is difficult to control, and when temperature was very low in the winter time, many melamine methylols aqueous solution can form milky white liquid, even forms nonhomogeneous system and be difficult to charging.For example Chinese patent CN1418899A is two-step approach.Chinese patent CN102010493A adopts two-step approach to prepare nitrogenous resol, this patent has at first prepared many melamine methylols, joining a large amount of phenol solutions then carries out copolycondensation again and prepares nitrogenous resol, the shortcoming of this method is that the stability of many melamine methylols on the one hand is difficult to control, when temperature is very low in the winter time, many melamine methylols aqueous solution can form milky white liquid, even forms nonhomogeneous system and be difficult to charging.A large amount of phenol will will remove under reduced pressure in the process of the nitrogenous resol of preparation on the other hand, contain the waste water that phenol contains aldehyde in a large number and not only can cause the pollution of environment, and can increase production cost simultaneously.About existing other patent reports of nitrogenous resol, reported a kind of preparation method of nitrogenous resol as Chinese patent CN1803873A, but this method only is applicable to the preparation of the resol of nitrogen content 5%.
Summary of the invention
The objective of the invention is to: at the shortcoming of above-mentioned prior art existence, the nitrogenous resol preparation method of a kind of one-step synthesis is proposed, this method adopts and adds copolycondensation monomer reaction rate adaptation agent and solvent, need not dewater, and can directly obtain nitrogenous phenol resin solution.
In order to realize purpose of the present invention, the nitrogenous resol preparation method of one-step synthesis of the present invention is:
Prepare the component of following mass parts:
Phenol 100
Guanamines 20～45
Formaldehyde or Paraformaldehyde 96 30～45
Catalyzer 1-2
Speed of reaction conditioning agent 2-5
Solvent 60-80
During preparation, the phenol of pre-heat fusing is added reactor, then add catalyzer, add 15-25 part formaldehyde or Paraformaldehyde 96 then, add speed of reaction conditioning agent and solvent again, insulation (being generally 0.5-1 hour) after the warming while stirring to 80 ℃ adds residual formaldehyde or Paraformaldehyde 96, insulation (being generally 2～5 hours) namely obtains nitrogenous phenol resin solution after being warming up to 100 ℃.
Phenol in the said components is the phenol of mass parts 100:0～100: alkyl-substituted phenols, wherein alkyl-substituted phenols is a kind of in p-cresol, ortho-cresol and the p-tert-butylphenol, preferred p-cresol.During preparation, with phenol and the alkyl-substituted phenols employing vacuum mode sucting reaction still of pre-heat fusing.
Catalyzer in the said components is at least a in ammoniacal liquor, sodium hydroxide and the triethylamine.
The guanamines of said components is trimeric cyanamide or trimeric cyanamide phenyl list substituent.
Speed of reaction conditioning agent in the said components is a kind of in ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, methyl ethyl ketone or the hexone.
Solvent in the said components is at least a in ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, methyl ethyl ketone (MEK) or the hexone (MIBK).
In brief, the present invention adopts phenol or contraposition and ortho position substituted alkyl phenol, formaldehyde and guanamines class monomer, be under the basic catalyst catalytic condition of 8-10 in the pH value, prepare nitrogenous phenol resin solution by a step copolycondensation, phenol wherein: guanamines: the mass ratio of formaldehyde is 100:20～45:30～45, and phenol: the mass ratio of alkyl-substituted phenols is 100:0～100, add the rate adaptation agent of copolycondensation monomer reaction and solvent simultaneously, under normal pressure, carry out copolycondensation in 80～100 ℃, 2～5 hours reaction times, need not dewater, directly obtain the nitrogenous phenol resin solution of homogeneous phase of stable storing.
Compared with prior art, the present invention is because the strong solvent of hydroxyl ether solvent turns usefulness into, make hydroxyl ether solvent, trimeric cyanamide and aldehyde form the middle transition state, effectively reduce the reactive behavior of trimeric cyanamide and formaldehyde, fully adjusted the copolycondensation speed of phenol, alkyl-substituted phenols and trimeric cyanamide and formaldehyde, made prepared cyanurotriamide modified phenol resin solution stable.This nitrogenous phenol resin solution is the solution that contains certain water, ethers and ketones solvent that generates at copolycondensation, has good consistency with Resins, epoxy, phosphorous epoxy resin and o-cresol formaldehyde epoxy resin.
Advantage of the present invention comprises: the ⑴ preparation method is simple, is easy to suitability for industrialized production; ⑵ can directly prepare nitrogenous phenol resin solution, guarantees in the whole process of production without any pollution, is the preparation method of compliance with environmental protection requirements; ⑶ the nitrogenous phenol resin solution that prepare and Resins, epoxy, phosphorous epoxy resin and benzoxazine resin have good consistency, be the environmentally friendly flame retardant type solidifying agent of Resins, epoxy, phosphorous epoxy resin and benzoxazine resin, can be widely used in the copper-clad plate industry.After the application, because system forms the P-N synergistic effect, therefore can reach desirable flame retardant effect, effectively reduce the consumption of phosphorous epoxy resin.
Embodiment
Further specify the nitrogenous resol preparation method of one-step synthesis of the present invention by the following examples.Illustrated embodiment does not limit content of the present invention.
Embodiment 1
The phenol of the pre-heat fusing of 100 grams is adopted vacuum mode sucting reaction still, then successively add 1.5 gram triethylamines, 40 gram trimeric cyanamides and 20 gram Paraformaldehyde 96s, 75 gram speed of reaction conditioning agent and solvents---wherein the ethylene glycol monomethyl ether 5 as the speed of reaction conditioning agent restrains, methyl ethyl ketone 70 grams as solvent, warming while stirring to 80 ℃, be incubated 0.5 hour, add 20 gram residue Paraformaldehyde 96s, then be warming up to 100 ℃, be incubated 3 hours, namely obtain nitrogenous phenol resin solution, this solution solid content 58-62%, hydroxyl equivalent is 130-150 and nitrogen content about 16.5%.
Get 35 parts of phosphorus contents and be 3% Resins, epoxy, 30 parts of o-cresol formaldehyde epoxy resins, 35 parts of nitrogenous resol, 18 parts of aluminium hydroxide, an amount of 2-methyl 4-ethyl imidazol(e), compound is solidified by certain technology, obtain the fire-retarded epoxy resin mixture, it is carried out flame retardant resistance UL94 test, and the experimental result demonstration reaches the V-0 level.
Embodiment 2
The phenol of the pre-heat fusing of 60 grams and the p-cresol of the pre-heat fusing of 40 grams are adopted vacuum mode sucting reaction still, then successively add 1.5 gram ammoniacal liquor, 31 gram trimeric cyanamides (or trimeric cyanamide phenyl list substituent) and 15 gram Paraformaldehyde 96s, 75 gram speed of reaction conditioning agent and solvents---wherein the propylene glycol monomethyl ether 3 as the speed of reaction conditioning agent restrains, hexone 72 grams as solvent, warming while stirring to 80 ℃, be incubated 1 hour, add 20 gram residue Paraformaldehyde 96s, then be warming up to 100 ℃, be incubated 5 hours, namely obtain nitrogenous phenol resin solution, this solution solid content 58-62%, hydroxyl equivalent is 130-150 and nitrogen content about 14.0%.
Get 35 parts of phosphorus contents and be 3% Resins, epoxy, 30 parts of o-cresol formaldehyde epoxy resins, 35 parts of nitrogenous resol, 18 parts of aluminium hydroxide, an amount of triphenyl phosphorus, compound is solidified by certain technology, obtain the fire-retarded epoxy resin mixture, it is carried out flame retardant resistance UL94 test, and the experimental result demonstration reaches the V-0 level.
Embodiment 3
The phenol of the pre-heat fusing of 50 grams and the ortho-cresol of the pre-heat fusing of 50 grams are adopted vacuum mode sucting reaction still, then successively add 1.5 gram sodium hydroxide, 25 gram trimeric cyanamides and 20 gram formaldehyde, 5 gram speed of reaction conditioning agent ethylene glycol ethyl ethers and 75 grams are as the mixed solvent of propylene glycol monomethyl ether/methyl ethyl ketone=1/1 of solvent, warming while stirring to 80 ℃, be incubated 0.5 hour, add 20 gram residual formaldehydes, then be warming up to 100 ℃, be incubated 4 hours, namely obtain nitrogenous phenol resin solution, this solution solid content 58-62%, hydroxyl equivalent is 130-150 and nitrogen content about 14.0%.
Getting 35 parts of phosphorus contents is 3% Resins, epoxy, 30 parts of o-cresol formaldehyde epoxy resins, 35 parts of nitrogenous resol, 18 parts of aluminium hydroxides, an amount of 2-methyl 4-ethyl imidazol(e) and an amount of triphenyl phosphorus, compound is solidified by certain technology, obtain the fire-retarded epoxy resin mixture, it is carried out flame retardant resistance UL94 test, and the experimental result demonstration reaches the V-0 level.
Embodiment 4
Adopt vacuum mode sucting reaction still in the p-tert-butylphenol with the phenol of the pre-heat fusing of 30 grams and the pre-heat fusing of 70 grams, then successively add 1.5 gram triethylamines, 31 gram trimeric cyanamides and 25 gram Paraformaldehyde 96s, 5 the gram speed of reaction conditioning agent hexones and as solvent 65 the gram propylene glycol monomethyl ether/hexone=1/1 mixed solvent, warming while stirring to 80 ℃, be incubated 0.5 hour, add 20 gram residual formaldehydes, then be warming up to 100 ℃, be incubated 3 hours, namely obtain nitrogenous phenol resin solution, this solution solid content 58-62%, hydroxyl equivalent is 130-150 and nitrogen content about 14.0%.
Getting 35 parts of phosphorus contents is 3% Resins, epoxy, 30 parts of o-cresol formaldehyde epoxy resins, 35 parts of nitrogenous resol, 18 parts of aluminium hydroxides, an amount of 2-methyl 4-ethyl imidazol(e) and an amount of triphenyl phosphorus, compound is solidified by certain technology, obtain the fire-retarded epoxy resin mixture, it is carried out flame retardant resistance UL94 test, and the experimental result demonstration reaches the V-0 level.
Claims (7)
1. the nitrogenous resol preparation method of one-step synthesis is characterized in that: the component of preparing following mass parts:
Phenol 100
Guanamines 20～45
Formaldehyde or Paraformaldehyde 96 30～45
Catalyzer 1-2
Speed of reaction conditioning agent 2-5
Solvent 60-80
During preparation, the phenol of pre-heat fusing is added reactor, then add catalyzer, add 15-25 part formaldehyde or Paraformaldehyde 96 then, add speed of reaction conditioning agent and solvent again, insulation after the warming while stirring to 80 ℃ adds residual formaldehyde or Paraformaldehyde 96, insulation namely obtains nitrogenous phenol resin solution after being warming up to 100 ℃.
2. the nitrogenous resol preparation method of one-step synthesis according to claim 1 is characterized in that: insulation is 0.5-1 hour after being warming up to 80 ℃, is incubated 2～5 hours after being warming up to 100 ℃.
3. the nitrogenous resol preparation method of one-step synthesis according to claim 1 and 2, it is characterized in that: the phenol in the described component is the phenol of mass parts 100:0～100: alkyl-substituted phenols, described alkyl-substituted phenols is a kind of in p-cresol, ortho-cresol and the p-tert-butylphenol, during preparation, with phenol and the alkyl-substituted phenols employing vacuum mode sucting reaction still of pre-heat fusing.
4. the nitrogenous resol preparation method of one-step synthesis according to claim 1 and 2 is characterized in that: the catalyzer in the described component is at least a in ammoniacal liquor, sodium hydroxide and the triethylamine.
5. the nitrogenous resol preparation method of one-step synthesis according to claim 1 and 2, it is characterized in that: the guanamines of described component is trimeric cyanamide or trimeric cyanamide phenyl list substituent.
6. the nitrogenous resol preparation method of one-step synthesis according to claim 1 and 2 is characterized in that: the speed of reaction conditioning agent in the described component is a kind of in ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, methyl ethyl ketone or the hexone.
7. the nitrogenous resol preparation method of one-step synthesis according to claim 1 and 2 is characterized in that: the solvent in the described component is at least a in ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, methyl ethyl ketone or the hexone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945600A (en) * | 2015-07-17 | 2015-09-30 | 史铁钧 | Epoxy curing agent containing alicyclic amine single benzoxazine and preparing method thereof |
| CN105694361A (en) * | 2016-03-17 | 2016-06-22 | 江苏文昌电子化工有限公司 | High-performance nitrogen-containing phenolic resin and preparation method thereof |
| CN106626683A (en) * | 2016-11-26 | 2017-05-10 | 山东金宝科创股份有限公司 | Manufacturing method of halogen-free, phosphorus-free, environment-friendly and flame-retardant paper-based copper clad laminate |
| CN106795259A (en) * | 2014-10-01 | 2017-05-31 | Dic株式会社 | Composition epoxy resin and its solidfied material |
| CN112724346A (en) * | 2020-02-28 | 2021-04-30 | 杭摩新材料(嘉兴)有限公司 | Flame-retardant phenolic resin and preparation method and application thereof |
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| CN101508761A (en) * | 2009-03-13 | 2009-08-19 | 江苏文昌电子化工有限公司 | Process for preparing phenolic resin containing nitrogen |
| CN102443126A (en) * | 2011-09-02 | 2012-05-09 | 王博 | Low-temperature foaming phenolic resin, preparation method thereof and preparation method of modified phenolic foam |
| CN102585125A (en) * | 2012-02-17 | 2012-07-18 | 广州三则电子材料有限公司 | Method for preparing thermoset phenolic resin and method for preparing conductive slurry |
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2013
- 2013-05-17 CN CN201310184439XA patent/CN103254381A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508761A (en) * | 2009-03-13 | 2009-08-19 | 江苏文昌电子化工有限公司 | Process for preparing phenolic resin containing nitrogen |
| CN102443126A (en) * | 2011-09-02 | 2012-05-09 | 王博 | Low-temperature foaming phenolic resin, preparation method thereof and preparation method of modified phenolic foam |
| CN102585125A (en) * | 2012-02-17 | 2012-07-18 | 广州三则电子材料有限公司 | Method for preparing thermoset phenolic resin and method for preparing conductive slurry |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795259A (en) * | 2014-10-01 | 2017-05-31 | Dic株式会社 | Composition epoxy resin and its solidfied material |
| CN104945600A (en) * | 2015-07-17 | 2015-09-30 | 史铁钧 | Epoxy curing agent containing alicyclic amine single benzoxazine and preparing method thereof |
| CN104945600B (en) * | 2015-07-17 | 2017-08-29 | 史铁钧 | A kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof |
| CN105694361A (en) * | 2016-03-17 | 2016-06-22 | 江苏文昌电子化工有限公司 | High-performance nitrogen-containing phenolic resin and preparation method thereof |
| CN105694361B (en) * | 2016-03-17 | 2018-04-06 | 江苏文昌电子化工有限公司 | High-performance Nitrogen-containing Phenolic Resins and preparation method thereof |
| CN106626683A (en) * | 2016-11-26 | 2017-05-10 | 山东金宝科创股份有限公司 | Manufacturing method of halogen-free, phosphorus-free, environment-friendly and flame-retardant paper-based copper clad laminate |
| CN112724346A (en) * | 2020-02-28 | 2021-04-30 | 杭摩新材料(嘉兴)有限公司 | Flame-retardant phenolic resin and preparation method and application thereof |
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Application publication date: 20130821 |