CN104649907B - Polymerization Chinese catalpa oil, preparation method and the method with polymerization Chinese catalpa oil modified phenolic resin for phenol-formaldehyde resin modified - Google Patents
Polymerization Chinese catalpa oil, preparation method and the method with polymerization Chinese catalpa oil modified phenolic resin for phenol-formaldehyde resin modified Download PDFInfo
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- CN104649907B CN104649907B CN201410766957.7A CN201410766957A CN104649907B CN 104649907 B CN104649907 B CN 104649907B CN 201410766957 A CN201410766957 A CN 201410766957A CN 104649907 B CN104649907 B CN 104649907B
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- chinese catalpa
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- 240000004528 Catalpa ovata Species 0.000 title claims abstract description 93
- 235000010005 Catalpa ovata Nutrition 0.000 title claims abstract description 93
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009413 insulation Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 61
- 235000019198 oils Nutrition 0.000 description 61
- 239000002383 tung oil Substances 0.000 description 13
- 239000003549 soybean oil Substances 0.000 description 12
- 235000012424 soybean oil Nutrition 0.000 description 12
- 239000012745 toughening agent Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 244000146553 Ceiba pentandra Species 0.000 description 2
- 235000003301 Ceiba pentandra Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- -1 price is cheaper Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The invention discloses a kind of polymerization Chinese catalpa oil, preparation method and method with polymerization Chinese catalpa oil modified phenolic resin for phenol-formaldehyde resin modified, described polymerization Chinese catalpa oil is that oily the reaction with maleic anhydride in epoxy Chinese catalpa is prepared from, by added amines catalyst epoxy Chinese catalpa oil with maleic anhydride according to 95～97:3～5 mass ratio, add and organic solvent dissolves mixing, it it is 110 DEG C～120 DEG C in reaction temperature, insulation reaction 2h～3h, obtain for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.Polymerization Chinese catalpa oil and epoxy resin being mixed according to the mass ratio of 1～2:5～12, join in absolute ethyl alcohol, be warming up to 70～80 DEG C, be completely dissolved to phenolic resin, be cooled to 45～55 DEG C, add curing agent, after to be solidified dose dissolves, cooling obtains phenol-formaldehyde resin modified.The present invention is used for phenol-formaldehyde resin modified, and production cost is low compared to existing technology, modified good product performance, of many uses.
Description
Technical field
The present invention relates to toughener technical field, be specifically related to a kind of technology be polymerized Chinese catalpa oil toughener and use polymerization Chinese catalpa oil modified phenolic resin.
Background technology
Copper-clad plate is the important materials of printed circuit board industry.The copper-clad plate prepared with pure resin shows the shortcomings such as goods are brittle, water imbibition is big, electrical insulation properties is on the low side, so being typically modified resin with toughener.
The advantages such as paper matrix material copper-clad plate, when making printed wiring board, has punching good, cheap, are therefore widely used.The manufacture process of paper-based copper-coated board is: be modified phenolic resin with drying oil (mainly tung oil), then by kapok paper gluing, is dried, obtains prepreg.After being overlapped according to the sheet number of regulation by prepreg, again carry out compound with Copper Foil heats the prepared paper-based copper-coated board of pressurization.
But the tung oil production cycle is long, the impact of yield and quality climate, season and region is very big, and resource quantity is very limited.In recent years, there is big landslide in domestic tung oil yield, year tung oil yield dropped to about 50,000 tons by original l0 ten thousand tons, 2009-2010 drops in production over a large area, and causes market to create multinomial the new highest record in history, and tung oil price creates the historical price of 25000 yuan/ton.Tung oil yield, the instability of price have the highest risk for the copper-clad plate industry depending on tung oil-modified toughened resin.
The most nontoxic, the environment-friendly type toughener that are currently known are epoxidized soybean oils, but owing to the basic material of epoxidized soybean oil is soybean oil, the major consumers market of soybean oil is still at field of food at present, therefore affected the biggest by field of food market price fluctuations, with general fine chemicals price fluctuation rule very different, therefore in the urgent need to a kind of alternative epoxidized soybean oil in actual production, price and production capacity are the most stable, nontoxic, the toughener of environment-friendly type.
Therefore, find a kind of toughener substitute products that can substitute tung oil or epoxidized soybean oil, reduce copper-clad plate production cost, improve product quality, improve the market competitiveness, be the most very necessary.
Present inventor is devoted to the research of copper-clad plate toughener for many years, through a large amount of theory analysises, market survey and experimental study, determine and can replace tung oil and epoxidized soybean oil with polymerization Chinese catalpa oil, it is primarily due to Chinese catalpa oil and has more unrighted acid, the configuration of unsaturated bond suitably incorporates active function groups, and the polymerization Chinese catalpa oil prepared under certain conditions can be used for the modification of phenolic resin；On the other hand, Chinese tallow tree has in China to be planted widely, and therefore oil resource in Chinese catalpa is sufficient, and price is less expensive compared with tung oil, is affected little by market price fluctuations relative to soybean oil.
Summary of the invention
First to be solved by this invention technical problem is that: the deficiency existed for prior art, there is provided a kind of for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, for substituting tung oil of the prior art and epoxidized soybean oil toughener, to solve existing toughener product price height, the technical problem of market unsettled.
Second to be solved by this invention technical problem is that: the deficiency existed for prior art, the preparation method of a kind of polymerization Chinese catalpa oil for phenol-formaldehyde resin modified is provided, this preparation method is simple, technique is easily controlled, the polymerization Chinese catalpa oil that it is prepared can be used for substituting tung oil of the prior art and epoxidized soybean oil toughener, to solve existing toughener product price height, the technical problem of market unsettled.
3rd to be solved by this invention technical problem is that: the deficiency existed for prior art, the method providing a kind of polymerization Chinese catalpa oil modified phenolic resin, to solve the problem that copper-clad plate production cost is high, market supply is unstable using tung oil or epoxidized soybean oil product price height to cause in prior art.
For solving above-mentioned first technical problem, the technical scheme is that
For the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, described polymerization Chinese catalpa oil is that oily the reaction with maleic anhydride in epoxy Chinese catalpa is prepared from.
Improving as one, described epoxy Chinese catalpa oil is the epoxy Chinese catalpa oil having added amines catalyst；Oily and described maleic anhydride the reaction mass ratio in the described epoxy Chinese catalpa having added amines catalyst is 95～97:3～5.
As the preferred technical scheme of one, the addition of described amines catalyst is the 1～5wt% of described epoxy Chinese catalpa oil.
As the preferred technical scheme of one, described amines catalyst is the compound of the one or two kinds of of dicyandiamide, m-phenylene diamine (MPD), triethanolamine, dimethyl benzylamine, dimethylaniline.
For solving above-mentioned second technical problem, the technical scheme is that
Preparation method for the polymerization Chinese catalpa oil of phenol-formaldehyde resin modified, comprise the following steps: by added amines catalyst epoxy Chinese catalpa oil with maleic anhydride according to 95～97:3～5 mass ratio, add and organic solvent dissolves mixing, it it is 110 DEG C～120 DEG C in reaction temperature, insulation reaction 2h～3h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
As the preferred technical scheme of one, the addition of described amines catalyst is the 1～5wt% of described epoxy Chinese catalpa oil.
As the preferred technical scheme of one, described amines catalyst is the compound of the one or two kinds of of dicyandiamide, m-phenylene diamine (MPD), triethanolamine, dimethyl benzylamine, dimethylaniline.
As the preferred technical scheme of one, described organic solvent selects at least one in ethanol, methyl alcohol, acetone.
As the preferred technical scheme of one, the consumption of described organic solvent is 1～3 times of weight of described epoxy Chinese catalpa oil consumption.
For solving above-mentioned 3rd technical problem, the technical scheme is that
A kind of method using polymerization Chinese catalpa oil modified phenolic resin, comprise the steps of and described polymerization Chinese catalpa oil and phenolic resin are mixed according to the mass ratio of 1～2:5～12, join in absolute ethyl alcohol, it is warming up to 70～80 DEG C, it is completely dissolved to phenolic resin, is cooled to 45～55 DEG C, add curing agent, after to be solidified dose dissolves, cooling obtains described phenol-formaldehyde resin modified.
As the preferred technical scheme of one, described curing agent is hexa, and the addition of described curing agent is the 3～6wt% of described phenolic resin.
As the preferred technical scheme of one, the consumption of described absolute ethyl alcohol is 1.5～3 times of weight of described phenolic resin.
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
The present invention is for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, use epoxy Chinese catalpa oil to react with maleic anhydride to be prepared from, owing to Chinese catalpa oil phase is than tung oil of the prior art and epoxidized soybean oil, price is cheaper, raw material is easy to get, market supply is stable, with polymerization Chinese catalpa oil modified phenolic resin, greatly reduces the production cost of copper-clad plate.
The present invention is for the preparation method of the polymerization Chinese catalpa oil of phenol-formaldehyde resin modified, and technique is simple, is easily controlled, and the polymerization Chinese catalpa oil of production is used for phenol-formaldehyde resin modified, and modified good product performance is of many uses.
When the polymerization Chinese catalpa oil of the present invention is used as the toughener of paper-based copper-coated board, owing to introducing flexible group, toughness increases substantially, and modified product has that punching performance is good and the advantage such as appearance color is shallow.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
For the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, described polymerization Chinese catalpa oil is that oily the reaction with maleic anhydride in epoxy Chinese catalpa is prepared from.
Embodiment 2
For the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, described polymerization Chinese catalpa oil be the epoxy Chinese catalpa oil having added amines catalyst be that 96:3 reacts and is prepared from maleic anhydride according to mass ratio, the addition of described amines catalyst is the 3.5wt% that described epoxy Chinese catalpa is oily.
Embodiment 3
For the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, described polymerization Chinese catalpa oil be the epoxy Chinese catalpa oil having added amines catalyst triethanolamine be that 97:4 reacts and is prepared from maleic anhydride according to mass ratio, the addition of described amines catalyst triethanolamine is the 3wt% that described epoxy Chinese catalpa is oily.
Embodiment 4
In 100ml there-necked flask, the epoxy Chinese catalpa oil 48g of 2wt% amines catalyst m-phenylene diamine (MPD) and dimethyl benzylamine will be added, with maleic anhydride 1.6g, add and organic solvent dissolves mixing, it is 112 DEG C in reaction temperature, insulation reaction 3h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
Embodiment 5
Amines catalyst dicyandiamide and the dimethylaniline of the 2.5wt% of epoxy Chinese catalpa oil is added in just preparing epoxy Chinese catalpa oil, in 100ml there-necked flask, the epoxy Chinese catalpa oil 32g of amines catalyst will have been added, with maleic anhydride 1g, join and absolute ethyl alcohol dissolves mixing, it is 116 DEG C in reaction temperature, insulation reaction 2.5h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
Embodiment 6
The amines catalyst triethanolamine of the 1.5wt% of epoxy Chinese catalpa oil is added in the epoxy Chinese catalpa oil just prepared, in 200ml there-necked flask, the epoxy Chinese catalpa oil 50g of amines catalyst will have been added, with maleic anhydride 1.5g, join and 60g absolute ethyl alcohol dissolves mixing, it is 110 DEG C in reaction temperature, insulation reaction 3h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
Being mixed by polymerization Chinese catalpa oil 18g and phenolic resin 60g, join in absolute ethyl alcohol, be warming up to 72 DEG C, be completely dissolved to phenolic resin, be cooled to 48 DEG C, add curing agent, after to be solidified dose dissolves, cooling obtains described phenol-formaldehyde resin modified.
Embodiment 7
Amines catalyst dimethyl benzylamine and the dimethylaniline of the 4.5wt% of epoxy Chinese catalpa oil is added in the epoxy Chinese catalpa oil just prepared, in 200ml there-necked flask, the epoxy Chinese catalpa oil 50g of amines catalyst will have been added, with maleic anhydride 2g, join and 75g acetone dissolves mixing, it is 120 DEG C in reaction temperature, insulation reaction 2.5h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
Polymerization Chinese catalpa oil 15g and phenolic resin 100g is mixed, joins in 200g absolute ethyl alcohol, be warming up to 80 DEG C, it is completely dissolved to phenolic resin, is cooled to 50 DEG C, add the hexa of the 4wt% of phenolic resin, after hexa dissolves, cooling obtains described phenol-formaldehyde resin modified.
Embodiment 8
Amines catalyst dicyandiamide and the m-phenylene diamine (MPD) of the 2wt% of epoxy Chinese catalpa oil is added in the epoxy Chinese catalpa oil just prepared, in 500ml there-necked flask, the epoxy Chinese catalpa oil 97g of amines catalyst will have been added, with maleic anhydride 4.5g, join and 200g absolute ethyl alcohol dissolves mixing, it is 115 DEG C in reaction temperature, insulation reaction 2.5h, obtain described for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
The polymerization Chinese catalpa oil 10g obtained and phenolic resin 50g is mixed, join in 120g absolute ethyl alcohol, it is warming up to 75 DEG C, it is completely dissolved to phenolic resin, it is cooled to 45 DEG C, adding the hexa of the 3.5wt% of phenolic resin, after hexa dissolves, cooling obtains described phenol-formaldehyde resin modified.
The modified alkyd resin glue liquid that above-described embodiment 6, embodiment 7 and embodiment 8 are prepared, respectively with the kapok paper impregnation cut out in advance, respectively obtain the sample after impregnation 1, sample 2 and sample 3, then sample is put into and be dried in baking oven, thus obtain prepreg.The prepreg of certain number is folded, puts into tablet press machine and carry out pressing plate.The laminate prepared is punched out the Indexs measure such as performance, bending strength, specific volume resistance to it, and visually observes the color regime to the laminate suppressed, and its performance indications situation is shown in Table 1.
Table 1
| Project | Unit | Sample 1 | Sample 2 | Sample 3 |
| Spread | % | 48.51 | 49.04 | 47.80 |
| Laminate thickness | mm | 1.58 | 1.62 | 1.60 |
| Specific insulation | 1010Ω·cm | 3.76 | 5.90 | 34.50 |
| Bending strength | Mpa | 199 | 230 | 207 |
| Punching | — | 4 grades | 5 grades | 5 grades |
| Outward appearance | Light yellow | Light yellow | Light yellow |
After the flow processs such as data can draw from table, is preparing through prepreg, pressing plate, sample 1-sample 3 all disclosure satisfy that in terms of specific insulation, bending strength, punching, appearance color electronic circuit board produces and the requirement of application.
Claims (9)
1. for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, it is characterised in that: described polymerization Chinese catalpa oil is epoxy Chinese catalpa oil and horse
Come what anhydride reaction was prepared from；Described epoxy Chinese catalpa oil is the epoxy Chinese catalpa oil having added amines catalyst；Described
Having added oily and described maleic anhydride the reaction mass ratio in the epoxy Chinese catalpa of amines catalyst is 95～97:3～5.
2. as claimed in claim 1 for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil, it is characterised in that: described amine
The addition of catalyst is the 1～5wt% of described epoxy Chinese catalpa oil.
3. for the preparation method being polymerized Chinese catalpa oil of phenol-formaldehyde resin modified, it is characterised in that comprise the following steps: will add
The epoxy Chinese catalpa oil of amines catalyst according to the mass ratio of 95～97:3～5, adds organic with maleic anhydride
Solvent dissolves mixing, is 110 DEG C～120 DEG C in reaction temperature, insulation reaction 2h～3h, obtain institute
State for the polymerization Chinese catalpa of phenol-formaldehyde resin modified oil.
4. the preparation method of the polymerization Chinese catalpa oil for phenol-formaldehyde resin modified as claimed in claim 3, it is characterised in that:
The addition of described amines catalyst is the 1～5wt% of described epoxy Chinese catalpa oil.
5. the preparation method of the polymerization Chinese catalpa oil for phenol-formaldehyde resin modified as claimed in claim 4, it is characterised in that:
Described amines catalyst is dicyandiamide, m-phenylene diamine (MPD), triethanolamine, dimethyl benzylamine, dimethylaniline
One or two kinds of compound.
6. the preparation method of the polymerization Chinese catalpa oil for phenol-formaldehyde resin modified as claimed in claim 3, it is characterised in that:
Described organic solvent selects at least one in ethanol, methyl alcohol, acetone.
7. the method with the polymerization Chinese catalpa oil modified phenolic resin described in claim 1, it is characterised in that comprise with
Lower step: described polymerization Chinese catalpa oil and phenolic resin are mixed according to the mass ratio of 1～2:5～12, adds
In absolute ethyl alcohol, it is warming up to 70～80 DEG C, is completely dissolved to phenolic resin, be cooled to 45～55 DEG C,
Adding curing agent, after to be solidified dose dissolves, cooling obtains described phenol-formaldehyde resin modified.
8. the method for polymerization Chinese catalpa as claimed in claim 7 oil modified phenolic resin, it is characterised in that: described solidification
Agent is hexa, and the addition of described curing agent is the 3～6wt% of described phenolic resin.
9. the method for polymerization Chinese catalpa as claimed in claim 7 oil modified phenolic resin, it is characterised in that: described anhydrous
The consumption of ethanol is 1.5～3 times of weight of described phenolic resin.
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| CN101531880A (en) * | 2009-04-28 | 2009-09-16 | 黑龙江省科学院石油化学研究院 | Canate-bimaleimide resin adhesive and preparation method |
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| CN101531880A (en) * | 2009-04-28 | 2009-09-16 | 黑龙江省科学院石油化学研究院 | Canate-bimaleimide resin adhesive and preparation method |
Non-Patent Citations (2)
| Title |
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| 植物油合成聚合物的研究进展;司徒粤等;《精细化工》;20061115;第23卷(第11期);第1045页右栏第2段-6.2半酯改性植物油聚酯 * |
| 环氧梓油的合成及其性质的研究;胡献安等;《郑州轻工业学院学报(自然科学版)》;19901212;第5卷(第04期);30-33 * |
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