CN101353405B - Method for modifying tung oil modified phenolic resin with melamine - Google Patents
Method for modifying tung oil modified phenolic resin with melamine Download PDFInfo
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- CN101353405B CN101353405B CN2008101506123A CN200810150612A CN101353405B CN 101353405 B CN101353405 B CN 101353405B CN 2008101506123 A CN2008101506123 A CN 2008101506123A CN 200810150612 A CN200810150612 A CN 200810150612A CN 101353405 B CN101353405 B CN 101353405B
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Abstract
The invention discloses a method for utilizing melamine to carry out modifying on tung-oil-modified phenolic resin. In the method, the melamine is adopted to carry out modification on the tung-oil-modified phenolic resin used by a secondary gel, which maintains the advantages of the tung-oil-modified phenolic resin and leads the resin after being modified to have a certain flame retardance. The method leads the manufacture technique of a flame retardant copper clad laminate to be changed from a double-dipping double-baking mode into a one-dipping one-baking mode, thus simplifying the manufacture technique flows and reducing the cost material. Compared with the traditional technique, the method of the invention mainly applies the melamine and a novel catalyst; while the production technique flows are not largely changed; new devices are not necessary to be increased. In addition, the newly selected catalyst is cheap and easily purchased which can not increase the cost of related products.
Description
Technical field
The invention belongs to the applied chemistry field, relate in a kind of paper-based copper-coated board technology with the manufacturing process of main resin especially a kind of method of tung oil modified phenolic resin being carried out modification with trimeric cyanamide.
Background technology
In making the phenolic aldehyde paper-based copper-coated board,, resin is carried out modification with pure phenolic resin so generally will be used for dry vegetable oil owing to show shortcomings such as goods are crisp firmly, water-absorbent is big, electrical insulation properties is on the low side.Consider that from over-all properties it have the title of " little epoxy " mostly to adopt tung oil that resin is carried out modification at present, the electrical insulation properties height after having that snappiness is good, water-intake rate is low, soak or make moist with its paper substrate copper coated foil plate of making, advantages such as low cost of manufacture.
Trimeric cyanamide is a kind of crystalline material, water insoluble, fusing point is 340 ℃, three primary aminos are arranged, they have active hydrogen atom, energy and aldehyde act as hydroxymethyl derivative, three amino on the trimeric cyanamide make it have very strong response capacity (six hydrogen atoms can both be replaced by aldehyde radical), the condensation in alkaline medium of trimeric cyanamide and formaldehyde forms thermosetting resin, this resin has higher physical strength, thermotolerance, flame retardant resistance, moisture resistivity and surface-discharge stability, be widely used in making molding powder, the strain insulator plastics, in paint and the laminated product, (trimeric cyanamide and formaldehyde react in out-phase because the reaction of trimeric cyanamide and formaldehyde is very complicated, reaction product is the trimeric cyanamide hydroxymethyl derivative, it can be water-soluble, water-soluble increasing and increase with the methylol quantity that is connected, in neutrality or weak alkaline medium, when formaldehyde is excessive, generate hexamethylolmelamine, it is the crystallized product of quite stable, and what this crystallized product can be good is soluble in water, and it can be separated out from water as PH=7, when hydrogen ion concentration reduces, can make the hexamethylolmelamine polycondensation form water-fast complicated polymkeric substance.Make normally per molecule trimeric cyanamide 3-3.5 molecule formaldehyde of terpolycyantoamino-formaldehyde resin, significantly reduction formaldehyde can not make reactant water-soluble to the ratio of trimeric cyanamide, thereby make terpolycyantoamino-formaldehyde resin to reactant ratio, reacting system PH value all has comparatively harsh requirement, this also is to cause the terpolycyantoamino-formaldehyde resin instability, be difficult to mix the major cause of using with other resins (G11 Resins, epoxy etc.), so all be to adopt two to soak two baking modes usually in the copper coated foil plate manufacturing, promptly use melamine resin as an impregnation resin separately, second time impregnation uses Resin adhesive by tung oil modified phenolic resin and fire retardant, toughner, compositions such as toning agent, but there is the technical process complexity in this operational path, require very high (must be two soak two baking modes) to producing automatic double surface gluer, the more high disadvantage of material cost.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of method of tung oil modified phenolic resin being carried out modification with trimeric cyanamide is provided, this method adopts trimeric cyanamide that two times glue are carried out modification with tung oil modified phenolic resin, kept the advantage of tung oil modified phenolic resin, and made the resin after the modification have certain flame retardant resistance.This method makes the manufacturing process of flame-proof cover copper foil plate change one into from the two two baking modes of soaking to soak a baking mode, simplified manufacturing process flow, reduced material cost.
The objective of the invention is to solve by the following technical programs:
This processing step that tung oil modified phenolic resin is carried out the method for modification with trimeric cyanamide is:
1) at first adding mass percent successively in reactor is 20%～33% phenol, 17%～23% tung oil and 0.1%～0.5% catalyzer a, opening vapour heats up, make temperature of charge be raised to 70 ℃～90 ℃, pick up counting, under this temperature, be incubated 70～110 minutes;
2) adding mass percent then in above-mentioned material is 1.5%～4% trimeric cyanamide, 20%～33% formaldehyde and 0.7%～1.3% catalyzer b, and be warmed up to 85 ℃～92 ℃, molding time, gel time are surveyed in sampling behind insulation reaction 30～60min under this temperature, it is 120s～150s that described gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, then continue under this temperature, to be incubated, qualified up to gel time;
3) qualified then beginning of gel time that records in above-mentioned found time, vacuum tightness will reach more than the 0.07MPa when finding time, when temperature of charge gos up 10 ℃～30 ℃ the time, get resin and survey gel time, if gel time is at 90s～130s, think that then gel time is qualified, releasing vacuum adding mass percent is 22%～33% solvent methanol, if defective then continuation of gel time found time up to qualified.
Above-mentioned catalyzer a is sulfuric acid, oxalic acid, hydrochloric acid, phthalic acid or suitable fourth dioctyl phthalate.
Above-mentioned catalyzer b is sodium hydroxide, hydrated barta, hexamethylenetetramine or ammoniacal liquor.
Above-mentioned methyl alcohol is industrial goods, and described tung oil is GB one-level tung oil, and described formaldehyde mass concentration is 37%.
The method that the present invention carries out modification with trimeric cyanamide to tung oil modified phenolic resin has been carried out suitable adjustment to former tung oil resin modified phenol formaldehyde resin synthesis technique, has selected new catalyst for use.Resin after the modification has certain flame retardant resistance, can reduce the consumption of brominated flame retardants such as high bromine epoxy as main production of resins flame retardant resistance copper coated foil plate with it, has both helped reducing product cost, helps guaranteeing the flame retardant properties of sheet material again.Sheet material color with this production of resins is faint yellow, and the sheet material color that modified resins is produced is a reddish-brown, covers Copper Foil with modified resin as the fire-retardant pattern flame retardant type of main production of resins, all can meet the correlation detection standard.
Than traditional technology, the present invention mainly has been to use trimeric cyanamide and new catalyst, and not bigger change of the technological process of production needn't increase new installation.Newly select catalyzer in addition, low price is easy to buying, can not improve the cost of related products.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to describe in further detail:
Embodiment 1
Start stirring, the industrial phenol that in reactor, adds 500kg successively, the one-level tung oil of 300kg and catalyzer-oxalic acid of 5kg, opening vapour heats up, make temperature of charge be raised to 81 ± 3 ℃, pick up counting, the trimeric cyanamide that after being incubated 70～110min under this temperature, adds 50kg, the formaldehyde of 500kg and catalyzer-sodium hydroxide of 20kg, and be warmed up to 85～92 ℃, molding time is surveyed in sampling behind insulation reaction 30～60min under this temperature, (gel time requires 160 ± 2 ℃ to gel time, the little skill in using a kitchen knife in cookery, 120～150s), it is (if defective to begin to find time after gel time is qualified, continuation is incubated under this temperature, and is qualified up to gel time), vacuum will reach more than the 0.07MPa when finding time, finding time approximately needs 2-4 hour, when temperature of charge goes back up to 10-30 ℃, after getting resin and surveying gel time (gel time require 90-130 second) gel time is qualified, remove vacuum and add solvent methanol (defective then continuation of gel time found time up to qualified).
Embodiment 2
Start stirring, the industrial phenol that in reactor, adds 600kg successively, the one-level tung oil of 400kg and catalyzer-oxalic acid of 7kg, opening vapour heats up, make temperature of charge be raised to 81 ± 3 ℃, pick up counting, the trimeric cyanamide that after being incubated 70～110min under this temperature, adds 70kg, the formaldehyde of 600kg and catalyzer-sodium hydroxide of 23kg, and be warmed up to 85～92 ℃, molding time is surveyed in sampling behind insulation reaction 30～60min under this temperature, (gel time requires 160 ± 2 ℃ to gel time, the little skill in using a kitchen knife in cookery, 120～150s), it is (if defective to begin to find time after gel time is qualified, continuation is incubated under this temperature, and is qualified up to gel time), vacuum will reach more than the 0.07MPa when finding time, finding time approximately needs 2-4 hour, when temperature of charge goes back up to 10-30 ℃, after getting resin and surveying gel time (gel time require 90-130 second) gel time is qualified, remove vacuum and add solvent methanol (defective then continuation of gel time found time up to qualified).
Embodiment 3
Start stirring, the industrial phenol that in reactor, adds 700kg successively, the one-level tung oil of 500kg and catalyzer-oxalic acid of 9kg, opening vapour heats up, make temperature of charge be raised to 81 ± 3 ℃, pick up counting, the trimeric cyanamide that after being incubated 70～110min under this temperature, adds 80kg, the formaldehyde of 700kg and catalyzer-sodium hydroxide of 25kg, and be warmed up to 85～92 ℃, molding time is surveyed in sampling behind insulation reaction 30～60min under this temperature, (gel time requires 160 ± 2 ℃ to gel time, the little skill in using a kitchen knife in cookery, 120～150s), it is (if defective to begin to find time after gel time is qualified, continuation is incubated under this temperature, and is qualified up to gel time), vacuum will reach more than the 0.07MPa when finding time, finding time approximately needs 2-4 hour, when temperature of charge goes back up to 10-30 ℃, after getting resin and surveying gel time (gel time require 90-130 second) gel time is qualified, remove vacuum and add solvent methanol (defective then continuation of gel time found time up to qualified).
Among the above embodiment be to the resin quality controlling index:
1. resin viscosity is controlled at 1600 ± 200CP (25 ℃), resin outward appearance homogeneous transparent;
2. resin gel time (160 ± 2 ℃, the little skill in using a kitchen knife in cookery, 90-130 second);
3. resin solid amount (50 ± 2%, 110 ℃, 2 hours).
Be described in detail doing below in conjunction with application example with the performance of the prepared resin of method of the present invention:
Application example 1: with this resin impregnation varnish(ed) paper, one side is covered each leading indicator of Copper Foil production CPFCP-04 (XPC) type copper-clad plate and is detected as follows:
Conclusion: measured result shows, with the sheet material of this production of resins, can satisfy the requirement of relevant criterion.
Embodiment 2: add a small amount of fire retardant at this resin, use and produce the copper-clad plate of CPFCP-09F (FR-1) type, each leading indicator test is as follows:
Conclusion: measured result shows, with the sheet material of this resin as main production of resins, can satisfy the requirement of relevant criterion.
Claims (4)
- One kind with trimeric cyanamide to the method that tung oil modified phenolic resin carries out modification, it is characterized in that carrying out according to following steps:1) at first adding mass percent successively in reactor is 20%～33% phenol, 17%～23% tung oil and 0.1%～0.5% catalyzer a, begin to heat up, make temperature of charge be raised to 70 ℃～90 ℃, pick up counting, under this temperature, be incubated 70～110 minutes; Described catalyzer a is sulfuric acid, oxalic acid, hydrochloric acid, phthalic acid or suitable fourth dioctyl phthalate;2) adding mass percent then in above-mentioned material is 1.5%～4% trimeric cyanamide, 20%～33% formaldehyde and 0.7%～1.3% catalyzer b, and be warmed up to 85 ℃～92 ℃, molding time and gel time are surveyed in sampling behind insulation reaction 30～60min under this temperature, it is 120s～150s that described gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, then continue under this temperature, to be incubated, qualified up to gel time; Described catalyzer b is sodium hydroxide, hydrated barta, hexamethylenetetramine or ammoniacal liquor;3) qualified then beginning of gel time that records in above-mentioned found time, vacuum tightness will reach more than the 0.07MPa when finding time, when temperature of charge gos up 10 ℃～30 ℃ the time, get resin and survey gel time, if gel time is at 90s～130s, think that then gel time is qualified, releasing vacuum adding mass percent is 22%～33% solvent methanol, if defective then continuation of gel time found time up to qualified.
- 2. according to claim 1 with trimeric cyanamide to the method that tung oil modified phenolic resin carries out modification, it is characterized in that: described methyl alcohol is industrial goods.
- 3. according to claim 1 with trimeric cyanamide to the method that tung oil modified phenolic resin carries out modification, it is characterized in that: described tung oil is GB one-level tung oil.
- 4. according to claim 1 with trimeric cyanamide to the method that tung oil modified phenolic resin carries out modification, it is characterized in that: described formaldehyde mass concentration is 37%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101506123A CN101353405B (en) | 2008-08-12 | 2008-08-12 | Method for modifying tung oil modified phenolic resin with melamine |
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| CN2008101506123A CN101353405B (en) | 2008-08-12 | 2008-08-12 | Method for modifying tung oil modified phenolic resin with melamine |
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| CN101353405B true CN101353405B (en) | 2011-06-29 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103113546B (en) * | 2013-01-28 | 2015-01-28 | 宜昌武星材料科技股份有限公司 | Self-lubricating multi-element copolymerized thermosetting resin and preparation method and application thereof |
| CN103122054A (en) * | 2013-02-19 | 2013-05-29 | 中国西电集团公司 | Method for modifying phenolic resin by using cardanol |
| CN103613906B (en) * | 2013-11-22 | 2015-07-15 | 江苏星源航天材料股份有限公司 | Flame-resistant melamine-paraformaldehyde modified tung oil resin for copper-clad plate |
| CN105330799B (en) * | 2015-11-13 | 2018-04-03 | 上海欧亚合成材料有限公司 | The preparation method of melamine, Cardanol Modified PF Resin |
| CN105542692B (en) * | 2015-12-17 | 2018-08-03 | 福建利豪电子科技股份有限公司 | A kind of manufacturing method of paper-based copper-coated board copper foil glue |
| CN106188448A (en) * | 2016-08-04 | 2016-12-07 | 中国西电集团公司 | Phenolic resin that a kind of epoxy soybean oil is modified and preparation method thereof |
| CN106750065A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of modified phenolic resin adhesive |
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Assignee: Xi'an Xidian electrical material Co., Ltd. Assignor: Xian Electric Manufacturing Corp. Contract record no.: 2012610000053 Denomination of invention: Method for modifying tung oil modified phenolic resin with melamine Granted publication date: 20110629 License type: Exclusive License Open date: 20090128 Record date: 20120504 |