CN110330612A - A kind of production technology of Novolac Cyanate Ester Resins - Google Patents
A kind of production technology of Novolac Cyanate Ester Resins Download PDFInfo
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- CN110330612A CN110330612A CN201910570021.XA CN201910570021A CN110330612A CN 110330612 A CN110330612 A CN 110330612A CN 201910570021 A CN201910570021 A CN 201910570021A CN 110330612 A CN110330612 A CN 110330612A
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- novolac cyanate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C261/00—Derivatives of cyanic acid
- C07C261/02—Cyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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Abstract
The present invention discloses a kind of production technology of Novolac Cyanate Ester Resins, it is the phenol structure that mono methoxy replaces that raw material Novolac Cyanate Eater Resin, which selects straight chain both ends, conventional methylene chloride is replaced with into water-soluble solvent acetone, tetrahydrofuran, dioxane, it is halogen-free, and Novolac Cyanate Eater Resin and catalyst of triethylamine are dissolved in solvent in advance and obtain mixed liquor, cyanogen chloride, which is dissolved in solvent, obtains mixed liquor, the flow-rate ratio of two kinds of mixed liquors of strict control, synthesis process avoids the introducing of halogen and the generation of by-product diethyl cyanamide, it is higher to solve residual halogens content in product, it is difficult to the problem of meeting the requirements the requirement of higher Halogen product.The naval stores that the present invention produces reaches 12min/200 DEG C through detecting gel time, and viscosity reaches 106mPaS, and glass transition temperature reaches 389 DEG C, chlorinity≤50PPM, diethyl cyanamide content≤0.5%.
Description
Technical field
The present invention relates to macromolecule resin synthesis technical fields, and in particular to a kind of production work of Novolac Cyanate Ester Resins
Skill.
Background technique
Cyanate is the reisn base material of a kind of high comprehensive performance, and Novolac Cyanate Eater Resin is one kind therein, be
Cyanate functional group (- OCN) is introduced on the skeleton of novolac, this kind of cyanate ester resin is keeping the same of excellent machinability
When, the very high glass transition temperature of product is assigned, can reach 400 DEG C or higher when being fully cured.Phenolic aldehyde in the prior art
The synthetic method of type cyanate is identical as other kinds of cyanate synthetic method, by under the catalysis of triethylamine, cyanogen halides
Nucleophilic substitution occurs with polyphenol and generates cyanate ester monomer resin, main reaction formula is as follows:
Wherein, n=1~7.
In actual be synthetically produced, other kinds of cyanate is compared in the synthesis of Novolac Cyanate Eater Resin, and synthesis is difficult, main
It wants the reason is that raw material phenolic resin itself is a kind of oligomer, the impurity that side reaction occurs on oligomer chain link and generates is difficult to
It is removed by the methods of purification, synthetic product purity is difficult to meet moulding process requirement.As domestic Novolac Cyanate Eater Resin synthesizes
The continuous maturation of technique is still deposited although having substantially met the market demand on yield and purity with international similar product
In gap.
A kind of Phenolic aralkyl cyanate resin of patent disclosure and its synthetic method of 102558471 A of publication No. CN,
It is obtained by catalyst preparation of trialkylamine, can satisfy high density printed circuit board baseplate material and high-performance composite materials
Application demand, however it remains following problems: 1. generally use methylene chloride, chloroform as solvent, it is difficult to which separation is complete, mistake
The catalyst of triethylamine of amount needs hydrochloric acid to be neutralized again, so that residual halogens content is higher in product, it is difficult to meet the requirements more
The requirement of high Halogen product is unable to reach the standard of chlorinity≤50PPM, diethyl cyanamide content≤0.5%；2. in product
One of Main By product diethyl cyanamide content it is higher, the presence of this by-product acts as the catalyst of polymerization reaction, mentions
Resin reaction activity is risen, the gel time of product is caused not reach requirement；Secondly the presence of the by-product directly affects product
Storage period.
Summary of the invention
In order to overcome above-mentioned technical problem, the purpose of the present invention is to provide a kind of productions of Novolac Cyanate Ester Resins
Technique, it is not halogen by the way that conventional methylene chloride is replaced with water-soluble solvent acetone, tetrahydrofuran, dioxane
Element, and Novolac Cyanate Eater Resin and catalyst of triethylamine are dissolved in solvent in advance and obtain mixed liquor, cyanogen chloride is dissolved in solvent
In obtain mixed liquor, the flow-rate ratio of two kinds of mixed liquors of strict control, synthesis process avoids introducing and the by-product two of halogen
The generation of ethyl cyanamide, solves in product that residual halogens content is higher, it is difficult to meet the requirements the requirement of higher Halogen product
The problem of；
Reaction temperature and reaction time are controlled in reaction process, are post-processed to use in purification process and are first filtered desalination,
Concentrated partial solvent-salt pickling-washing-addition ethyl acetate-liquid separation extraction-organic phase vacuum distillation-deionization washing again
- ethyl acetate dissolution-vacuum distillation multiple working procedure is washed, so that naval stores is largely dissolved in ethyl acetate, solvent, moisture
Completely, product yield high, while keeping excellent machinability, glass transition temperature, gel time meets the requirements for removal.
The purpose of the present invention can be achieved through the following technical solutions:
The present invention provides a kind of production technology of Novolac Cyanate Ester Resins, which is taken by methoxyl group
The Novolac Cyanate Eater Resin I and cyanogen chloride in generation synthesize under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, n is 2~7；
Production technology the following steps are included:
S1, methoxy-substituted Novolac Cyanate Eater Resin I, triethylamine are weighed according to molar ratio 1:1.2-1.3, be dissolved in organic
It in solvent a, is sufficiently stirred and makes it dissolve in the first mixing tank, be uniformly mixed and obtain mixed liquor a；
S2, organic solvent b, cyanogen chloride are passed through in the second mixing tank, are uniformly mixed in -20~-15 DEG C of insulated and stirreds
Close liquid b；Wherein, the additive amount of cyanogen chloride is 1.05-1.1 times of methoxy-substituted I mole of Novolac Cyanate Eater Resin；
S3, the first condenser, the first pneumatic diaphragm valve, the second pneumatic diaphragm valve are opened, so that mixed liquor a is pneumatic through first
Diaphragm valve reaches at flow-controlling meter, and mixed liquor b is cooled to -20~-15 DEG C through the first condenser, passes through the second pneumatic diaphragm valve
Reach at flow-controlling meter, mixed liquor a and mixed liquor b are passed through booster pump by flow-controlling meter, will be mixed after the pressurization of booster pump
It closes reaction solution to be passed through in automatic reactor, the reaction was continued in reaction kettle 3.2-3.5 hours；
S4, by the reaction system desalination in reaction kettle, obtain filtrate systems, filtrate systems enter in the first concentration tank, subtract
Pressure concentration obtains concentration filtrate after removing a part of solvent, be concentrated filtrate through salt pickling, be washed to neutrality after be passed through in extractor,
Appropriate ethyl acetate is added, after vibrating 5-10min, removes water phase after liquid separation extraction, retains organic phase；
S5, organic phase are passed through in the second concentration tank, and after vacuum distillation removes solvent, deionized water washing reuses second
Acetoacetic ester dissolution, after standing 30-50min, further vacuum distillation obtains product.
The production technology of Novolac Cyanate Ester Resins of the present invention, it is contemplated that traditional Novolac Cyanate Ester Resins product structure
It is single, basic structure is used as using the phenol of unsubstituted, is steamed after raw material low-temp reaction through simple filtration-pickling-washing-decompression
Evaporate rear getting the product.On the one hand without the charge ratio of strict control reaction temperature and raw material, so that side reaction largely carries out, it is secondary
Product is more and is difficult to remove clean；It is molten in extraction process when on the other hand using the water-soluble solvent of acetone, acetonitrile etc
Agent and water are miscible, removal water phase can not be extracted by liquid separation, a part of product can enter water phase, with vacuum distillation process one
Divide naval stores to steam with solvent, reduces product yield.
The present invention has carried out a large amount of screening to factors such as raw material, solvent, technical process, temperature, reaction ratio, flow-rate ratios
And experiment, it is the phenol structure that mono methoxy replaces that raw material Novolac Cyanate Eater Resin, which selects straight chain both ends, and methoxyl group has electrophilic
Inductive effect and supplied for electronic conjugation, wherein the conjugation of supplied for electronic is occupied an leading position, therefore shows as supplying on phenyl ring
Electronics, electron donating property is also bigger than methyl, while can activate the phenyl ring at straight chain both ends, improves the parent of negative oxygen ion on phenolic hydroxyl group
Nuclearity, improve with the selectivity reacted and reaction rate of cyanogen chloride, significantly improve reaction yield.
In terms of the selection of organic solvent, using one in acetone, tetrahydrofuran, dioxane, dimethylformamide, acetonitrile
Kind or a variety of compositions, these solvents and water have good compatibility, after dissolving raw material Novolac Cyanate Eater Resin, cyanogen chloride,
Material concentration can be diluted, the reaction rate of raw material, while the triethyl group chloramines salt that insoluble reaction generates are improved, so that three second
Base chloramines salt is deposited in reactor bottom；After filtering desalination, in order to divide organic phase and water phase preferably after salt pickling, washing
Layer simultaneously removes water phase, and the present invention is first concentrated under reduced pressure after filtering desalination, removes a part of water-soluble solvent, then carry out hydrochloric acid
It washes, wash, appropriate ethyl acetate is added and extracts a large amount of naval stores, since ethyl acetate and water can only be mixed partially
Molten, remaining water-soluble solvent can also infiltrate through most of naval stores of dissolution in the organic phase of ethyl acetate.Not only make
Water phase and organic phase separate more thorough, but also solubility of the naval stores in organic phase is more preferable, improve resin production
The yield of product.
Organic solvent, cyanogen chloride are added in reaction kettle by step S2, strict temperature control, equal in -20~-15 DEG C of stirrings
It is even to obtain mixed liquor, the reactivity of cyanogen chloride is reduced under low temperature；Reaction kettle is cooled to -20~-15 DEG C in advance by step S3, is made
Cyanogen chloride solution enter reaction kettle after temperature do not fluctuate and keep stable reactivity, efficiently and stably with phenol aldehyde type cyanic acid
Nucleophilic substitution occurs for ester.
As a further solution of the present invention, organic solvent a is acetone, tetrahydrofuran, dioxane, dimethyl formyl
One of amine, acetonitrile or a variety of compositions, additive amount be methoxy-substituted Novolac Cyanate Eater Resin I, triethylamine quality it
12-15 times of sum.
As a further solution of the present invention, organic solvent b is acetone, tetrahydrofuran, dioxane, dimethyl formyl
One of amine, acetonitrile or a variety of compositions, additive amount are 5-8 times of cyanogen chloride quality.
Organic solvent uses one of acetone, tetrahydrofuran, dioxane, dimethylformamide, acetonitrile or a variety of
Composition, these solvents and water have good compatibility, after dissolving raw material Novolac Cyanate Eater Resin, cyanogen chloride, can dilute original
Expect concentration, improves the reaction rate of raw material.
As a further solution of the present invention, the mass flow ratio of step S3 mixed liquor a and mixed liquor b addition reaction kettle is
22-50。
As a further solution of the present invention, step S4 filtrate systems, which are concentrated under reduced pressure, removes filtrate systems quality 1/3-1/2
Solvent；The additive amount of ethyl acetate is 3-5 times that filtrate quality is concentrated.
As a further solution of the present invention, step S5 deionized water washing times are 3-5 times；The additive amount of ethyl acetate
It is 1.5-2.5 times of organic phase quality.
As a further solution of the present invention, the automatic reactor is made of several reaction kettles, previous reaction kettle
Outlet tube connect with the inlet tube of the latter reaction kettle, the outlet tube of the last one reaction kettle is connected with filtering tank.
As a further solution of the present invention, be equipped with jet chimney at the top of the reaction kettle, jet chimney with master
Pipeline connection, one end of main pipeline are connect by the first shut-off valve, compressor with the inlet end of the second condenser, main pipeline it is another
One end is connect by the second shut-off valve with the outlet side of the second condenser；The main pipeline, the first shut-off valve, compressor, second
Condenser, the second shut-off valve are interconnected to form high/low temperature steam passage two-by-two.
Beneficial effects of the present invention:
1, the production technology of Novolac Cyanate Ester Resins of the invention, compared with the prior art in production technology, raw material,
A large amount of screening and experiment have been carried out in the factors such as solvent, technical process, temperature, reaction ratio, flow-rate ratio.By will be conventional
Methylene chloride replaces with water-soluble solvent acetone, tetrahydrofuran, dioxane, is halogen-free, and by phenol aldehyde type cyanic acid
Ester and catalyst of triethylamine are dissolved in solvent in advance obtains mixed liquor, and cyanogen chloride, which is dissolved in solvent, obtains mixed liquor, strictly
The flow-rate ratio of two kinds of mixed liquors is controlled, synthesis process avoids the introducing of halogen and the generation of by-product diethyl cyanamide；Instead
Reaction temperature and reaction time should be controlled in the process, are post-processed to use in purification process and are first filtered desalination, then concentrated portion
Divide solvent-salt pickling-washing-addition ethyl acetate-liquid separation extraction-organic phase vacuum distillation-deionized water washing-ethyl acetate
Dissolution-vacuum distillation multiple working procedure, so that naval stores is largely dissolved in ethyl acetate, solvent, moisture removal are complete, produce
Object high income, while keeping excellent machinability, glass transition temperature, gel time meets the requirements.Yield reaches 87%,
It is detected gel time and reaches 12min/200 DEG C, viscosity reaches 106mPaS, and glass transition temperature reaches 389 DEG C, and chlorine contains
Amount≤50PPM, diethyl cyanamide content≤0.5%.
2, it is the phenol structure that mono methoxy replaces that raw material Novolac Cyanate Eater Resin, which selects straight chain both ends, and methoxyl group, which has, inhales electricity
Sub- inductive effect and supplied for electronic conjugation, wherein the conjugation of supplied for electronic is occupied an leading position, therefore is shown as on phenyl ring
Supplied for electronic, electron donating property is also bigger than methyl, while can activate the phenyl ring at straight chain both ends, improves negative oxygen ion on phenolic hydroxyl group
Nucleophilicity, improve with the selectivity reacted and reaction rate of cyanogen chloride, significantly improve reaction yield.
3, organic solvent uses one of acetone, tetrahydrofuran, dioxane, dimethylformamide, acetonitrile or a variety of
Composition, these solvents and water have a good compatibility, after dissolution raw material Novolac Cyanate Eater Resin, cyanogen chloride, can dilute
Material concentration improves the reaction rate of raw material, while the triethyl group chloramines salt that insoluble reaction generates, so that triethyl group chloramines salt
It is deposited in reactor bottom；After filtering desalination, in order to make organic phase and water phase preferably be layered and remove after salt pickling, washing
Water phase.
4, by being first concentrated under reduced pressure after filtering desalination, a part of water-soluble solvent is removed, then carry out salt pickling, water
Wash, appropriate ethyl acetate be added and extracts a large amount of naval stores, due to ethyl acetate and water can only partial miscibility, it is remaining
Water-soluble solvent most of naval stores of dissolution can also be infiltrated through in the organic phase of ethyl acetate.Not only make water phase and has
Machine mutually separates more thorough, but also solubility of the naval stores in organic phase is more preferable, improves the yield of naval stores.
5, by the way that organic solvent, cyanogen chloride to be added in reaction kettle, strict temperature control is equal in -20~-15 DEG C of stirrings
It is even to obtain mixed liquor, the reactivity of cyanogen chloride is reduced under low temperature；Reaction kettle is cooled to -20~-15 DEG C in advance by step S3, is made
Cyanogen chloride solution enter reaction kettle after temperature do not fluctuate and keep stable reactivity, efficiently and stably with phenol aldehyde type cyanic acid
Nucleophilic substitution occurs for ester.
6, the production system of Novolac Cyanate Ester Resins of the present invention, the hot steam that exothermic heat of reaction generates can be along steam pipe
Road, main pipeline, the first shut-off valve enter in compressor, after compressor is to gas compression, into the second condenser in condense, it is low
The circulating condensing of mild high-temperature steam, can keep the constant low temperature environment in reaction kettle, keep the positive of reaction to carry out, reduce
The production rate of by-product.
Detailed description of the invention
The present invention will be further described below with reference to the drawings.
Fig. 1 is the structural schematic diagram of the production system of Novolac Cyanate Ester Resins of the present invention.
In figure: 1, reaction kettle；2, the first mixing tank；3, the second mixing tank；4, the first condenser；5, the second condenser；6,
Flow-controlling meter；7, the first pneumatic diaphragm valve；8, the second pneumatic diaphragm valve；9, filtering tank；10, the first concentration tank；11, it extracts
Tank；12, the second concentration tank；13, jet chimney；14, main pipeline；15, the first shut-off valve；16, compressor；17, the second shut-off valve；
18, booster pump.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 3 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 14.8g are weighed, is dissolved in 1607g acetonitrile, fills
Divide and stir to dissolve, is uniformly mixed and obtains mixed liquor a；
S2,54.6g acetone, 7.8g cyanogen chloride are uniformly obtained into mixed liquor b in -18 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -18 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.3 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 26.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 3.6 times of acetic acid of concentration filtrate quality is added
Ethyl ester, after vibrating 8min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2 times of organic phase quality of acetic acid second after deionized water washing
Ester dissolution, after standing 46min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 87%, purity 99.1% is 12min/200 through detection gel time
DEG C, viscosity is 106mPaS (25 DEG C), and glass transition temperature is 389 DEG C, chlorinity≤50PPM, diethyl cyanamide content≤
0.5%.
Embodiment 2
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 4 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 11.7g are weighed, is dissolved in 1452g dioxane
In, it is sufficiently stirred and makes it dissolve, be uniformly mixed and obtain mixed liquor a；
S2,45g dioxane, 6.0g cyanogen chloride are uniformly obtained into mixed liquor b in -16 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -16 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.4 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 29.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 4.6 times of acetic acid of concentration filtrate quality is added
Ethyl ester, after vibrating 7min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2.3 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 42min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 85.5%, purity 98.7% is 11.8min/ through detection gel time
200 DEG C, viscosity is 112mPaS (25 DEG C), and glass transition temperature is 385 DEG C, and chlorinity≤50PPM, diethyl cyanamide contains
Amount≤0.5%.
Embodiment 3
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 5 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 9.2g are weighed, is dissolved in 1365g dimethyl formyl
It in amine, is sufficiently stirred and makes it dissolve, be uniformly mixed and obtain mixed liquor a；
S2,39g dimethylformamide, 5g cyanogen chloride are uniformly obtained into mixed liquor b in -20 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -20 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.5 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 33.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 4.5 times of acetic acid of concentration filtrate quality is added
Ethyl ester, after vibrating 10min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2.3 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 46min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 85.2%, purity 98.5% is 11.2min/ through detection gel time
200 DEG C, viscosity is 99mPaS (25 DEG C), and glass transition temperature is 388 DEG C, chlorinity≤50PPM, diethyl cyanamide content
≤ 0.5%.
Embodiment 4
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 6 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 8.2g are weighed, is dissolved in 1623g acetone, fills
Divide and stir to dissolve, is uniformly mixed and obtains mixed liquor a；
S2,29.5g acetone, 4.1g cyanogen chloride are uniformly obtained into mixed liquor b in -15 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -15 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.2 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 47；
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 5 times of acetic acid second of concentration filtrate quality is added
Ester, after vibrating 9min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2.4 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 48min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 84.7%, purity 99.0% is 12.5min/ through detection gel time
200 DEG C, viscosity is 117mPaS (25 DEG C), and glass transition temperature is 397 DEG C, and chlorinity≤50PPM, diethyl cyanamide contains
Amount≤0.5%.
Embodiment 5
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 5 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 9.8g are weighed, is dissolved in 1603g acetonitrile, fills
Divide and stir to dissolve, is uniformly mixed and obtains mixed liquor a；
S2,32g acetonitrile, 4.9g cyanogen chloride are uniformly obtained into mixed liquor b in -18 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -18 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.4 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 46.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 5 times of acetic acid second of concentration filtrate quality is added
Ester, after vibrating 10min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 1.7 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 40min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 86.4%, purity 98.6% is 11.6min/ through detection gel time
200 DEG C, viscosity is 98mPaS (25 DEG C), and glass transition temperature is 385 DEG C, chlorinity≤50PPM, diethyl cyanamide content
≤ 0.5%.
Embodiment 6
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 4 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 11.4g are weighed, is dissolved in 1582g tetrahydrofuran
In, it is sufficiently stirred and makes it dissolve, be uniformly mixed and obtain mixed liquor a；
S2,46.5g tetrahydrofuran, 6.2g cyanogen chloride are uniformly obtained into mixed liquor b in -17 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -17 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.4 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 34.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 3.6 times of acetic acid of concentration filtrate quality is added
Ethyl ester, after vibrating 7min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2.4 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 47min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 85.4%, purity 98.8% is 11.5min/ through detection gel time
200 DEG C, viscosity is 102mPaS (25 DEG C), and glass transition temperature is 384 DEG C, and chlorinity≤50PPM, diethyl cyanamide contains
Amount≤0.5%.
Embodiment 7
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 5 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 9.8g are weighed, is dissolved in 1515g dimethyl formyl
It in amine, is sufficiently stirred and makes it dissolve, be uniformly mixed and obtain mixed liquor a；
S2,30g acetone, 4.8g cyanogen chloride are uniformly obtained into mixed liquor b in -20 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -20 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.4 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 45.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 4.3 times of acetic acid of concentration filtrate quality is added
Ethyl ester, after vibrating 10min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 2.5 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 43min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 84.9%, purity 98.4% is 12.2min/ through detection gel time
200 DEG C, viscosity is 100mPaS (25 DEG C), and glass transition temperature is 382 DEG C, and chlorinity≤50PPM, diethyl cyanamide contains
Amount≤0.5%.
Embodiment 8
The present embodiment provides a kind of production technologies of Novolac Cyanate Ester Resins, and the Novolac Cyanate Ester Resins are by methoxyl group
Substituted Novolac Cyanate Eater Resin I and cyanogen chloride synthesizes under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, 6 n；
Production technology the following steps are included:
S1, methoxy-substituted I 100g of Novolac Cyanate Eater Resin, triethylamine 8.3g are weighed, is dissolved in 1624g acetone, fills
Divide and stir to dissolve, is uniformly mixed and obtains mixed liquor a；
S2,30g acetone, 4.2g cyanogen chloride are uniformly obtained into mixed liquor b in -16 DEG C of insulated and stirreds；
S3, reaction kettle is cooled to -16 DEG C in advance, then mixed liquor a and mixed liquor b is separately added into reaction kettle, mixed
The reaction was continued after conjunction 3.5 hours；The mass flow ratio that reaction kettle is added in mixed liquor a and mixed liquor b is 47.
S4, it is filtered to remove the salt that reaction generates, obtains filtrate systems, be concentrated under reduced pressure and remove filtrate systems quality 1/3-1/2
Solvent, obtain concentration filtrate, concentration filtrate through salt pickling, be washed to neutrality, 5 times of acetic acid second of concentration filtrate quality is added
Ester, after vibrating 10min, liquid separation extraction removal water phase retains organic phase；
S5, organic phase vacuum distillation remove solvent and reuse 1.9 times of organic phase quality of acetic acid after deionized water washing
Ethyl ester dissolution, after standing 50min, vacuum distillation obtains product.
The product is brown oil liquid, and yield 85.8%, purity 98.2% is 11.2min/ through detection gel time
200 DEG C, viscosity is 98mPaS (25 DEG C), and glass transition temperature is 387 DEG C, chlorinity≤50PPM, diethyl cyanamide content
≤ 0.5%.
Embodiment 9
As shown in fig.1, present embodiments providing a kind of production system of Novolac Cyanate Ester Resins, it is suitable for above-mentioned reality
Apply the production technology of the Novolac Cyanate Ester Resins of a 1-8, including automatic reactor, the first mixing tank 2, the second mixing tank 3,
One condenser 4, the second condenser 5, flow-controlling meter 6；First mixing tank 2 is used for Novolac Cyanate Eater Resin I, triethylamine, You Jirong
The stirring and dissolving of agent a, the first mixing tank 2 are connect by the first pneumatic diaphragm valve 7 with flow-controlling meter 6.Second mixing tank 3 is used for
The mixing of acetonitrile, cyanogen chloride, the second mixing tank 3 are connect by the second pneumatic diaphragm valve 8 with flow-controlling meter 6, and first is mixed
Batch can 2 is arranged in parallel with the second mixing tank 3, and the first condenser 4 is equipped between the second mixing tank 3 and the second pneumatic diaphragm valve 8.Stream
Amount adjusts meter 6 and is connect by booster pump 18 with automatic reactor.Automatic reactor is made of several reaction kettles 1, previous anti-
The outlet tube of kettle and the inlet tube of the latter reaction kettle is answered to connect, the outlet tube of the last one reaction kettle is connected with filtering tank 9, mistake
Filter tank 9 is connected with the first concentration tank 10 by pipeline, and the first concentration tank 10 is connected with extractor 11 by pipeline, and extractor 11 is logical
Piping is connected with the second concentration tank 12.The top of reaction kettle 1 is equipped with jet chimney 13, jet chimney 13 with main pipeline 14
One end of connection, main pipeline 14 is connect by the first shut-off valve 15, compressor 16 with the inlet end of the second condenser 5, main pipeline
14 other end is connect by the second shut-off valve 17 with the outlet side of the second condenser 5.Main pipeline 14, the first shut-off valve 15, pressure
Contracting machine 16, the second condenser 5, the second shut-off valve 17 are interconnected to form high/low temperature steam passage two-by-two.
The course of work of the production system of the Novolac Cyanate Ester Resins is as follows: (1) by Novolac Cyanate Eater Resin and triethylamine
It is passed through in the first mixing tank 2, adds organic solvent a, being sufficiently stirred dissolves Novolac Cyanate Eater Resin and triethylamine, is mixed
Liquid a；(2) it is mixed evenly organic solvent b, cyanogen chloride to obtain mixed liquor b in the second mixing tank 3；(3) it is cold to open first
Condenser 4, the first pneumatic diaphragm valve 7, the second pneumatic diaphragm valve 8, so that mixed liquor a reaches flow tune through the first pneumatic diaphragm valve 7
At section meter 6, mixed liquor b is cooled to -20~-15 DEG C through the first condenser 4, reaches flow by the second pneumatic diaphragm valve 8 and adjusts
It counts at 6, mixed liquor a and mixed liquor b are passed through booster pump 18 according to mass flow ratio 22-50 by flow-controlling meter 6, through booster pump 18
Pressurization after mixed reaction solution is passed through in automatic reactor；(4) the second condenser 5, the first shut-off valve 15, compressor are opened
16, the second shut-off valve 17, the second condenser 5 generate -20~-15 DEG C of Low Temperature Steam, through the second shut-off valve 17, main pipeline 14,
Jet chimney 13, which enters in reaction kettle 1, reacts reaction system at low temperature；(5) hot steam that exothermic heat of reaction generates can
To enter in compressor 16 along jet chimney 13, main pipeline 14, the first shut-off valve 15, after compressor 16 is to gas compression, into
Entering condensation in the second condenser 5, the circulating condensing of low temperature and high-temperature steam can keep the constant low temperature environment in reaction kettle 1,
It keeps the positive of reaction to carry out, reduces the production rate of by-product.(6) after the reaction was completed, the reaction system in reaction kettle 1 is removed
Salt obtains filtrate systems, and filtrate systems enter in the first concentration tank 10, is concentrated under reduced pressure after removing a part of solvent and obtains concentration filter
Liquid, filtrate through salt pickling, be washed to neutrality after be passed through in extractor 11, be added appropriate ethyl acetate, after vibrating 5-10min, point
Water phase is removed after liquid extraction, retains organic phase, organic phase is passed through in the second concentration tank 12, after vacuum distillation removes solvent, is gone
Ion water washing reuses ethyl acetate dissolution, and after standing 30-50min, further vacuum distillation obtains product.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched
The specific embodiment stated does various modifications or additions or is substituted in a similar manner, and without departing from invention or surpasses
More range defined in the claims, is within the scope of protection of the invention.
Claims (8)
1. a kind of production technology of Novolac Cyanate Ester Resins, which is characterized in that the Novolac Cyanate Ester Resins are taken by methoxyl group
The Novolac Cyanate Eater Resin I and cyanogen chloride in generation synthesize under the catalysis of triethylamine, and reaction equation is as follows:
Wherein, n is 2~7；
Production technology the following steps are included:
S1, methoxy-substituted Novolac Cyanate Eater Resin I, triethylamine are weighed according to molar ratio 1:1.2-1.3, is dissolved in organic solvent
It in a, is sufficiently stirred and makes it dissolve in the first mixing tank (2), be uniformly mixed and obtain mixed liquor a；
S2, organic solvent b, cyanogen chloride are passed through in the second mixing tank (3), are uniformly mixed in -20~-15 DEG C of insulated and stirreds
Liquid b；Wherein, the additive amount of cyanogen chloride is 1.05-1.1 times of methoxy-substituted I mole of Novolac Cyanate Eater Resin；
S3, the first condenser (4), the first pneumatic diaphragm valve (7), the second pneumatic diaphragm valve (8) are opened, so that mixed liquor a is through the
One pneumatic diaphragm valve (7) reaches at flow-controlling meter (6), and mixed liquor b is cooled to -20~-15 DEG C through the first condenser (4), leads to
It crosses the second pneumatic diaphragm valve (8) to reach at flow-controlling meter (6), mixed liquor a and mixed liquor b are passed through increasing by flow-controlling meter (6)
Mixed reaction solution, is passed through in automatic reactor by press pump (18) after the pressurization of booster pump (18), continues in reaction kettle (1) anti-
It answers 3.2-3.5 hours；
S4, by the reaction system desalination in reaction kettle (1), obtain filtrate systems, filtrate systems enter in the first concentration tank (10),
Be concentrated under reduced pressure after removing a part of solvent and obtain concentration filtrate, be concentrated filtrate through salt pickling, be washed to neutrality after be passed through extractor
(11) in, appropriate ethyl acetate is added, after vibrating 5-10min, removes water phase after liquid separation extraction, retains organic phase；
S5, organic phase are passed through in the second concentration tank (12), and after vacuum distillation removes solvent, deionized water washing reuses second
Acetoacetic ester dissolution, after standing 30-50min, further vacuum distillation obtains product.
2. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that organic solvent a is third
One of ketone, tetrahydrofuran, dioxane, dimethylformamide, acetonitrile or a variety of compositions, additive amount take for methoxyl group
12-15 times of the Novolac Cyanate Eater Resin I in generation, triethylamine quality sum.
3. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that organic solvent b is third
One of ketone, tetrahydrofuran, dioxane, dimethylformamide, acetonitrile or a variety of compositions, additive amount are cyanogen chloride matter
5-8 times of amount.
4. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that step S3 mixed liquor a
It is 22-50 with the mixed liquor b mass flow ratio that reaction kettle is added.
5. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that step S4 filtrate systems
The solvent for removing filtrate systems quality 1/3-1/2 is concentrated under reduced pressure；The additive amount of ethyl acetate is 3-5 times that filtrate quality is concentrated.
6. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that step S5 deionized water
Washing times are 3-5 times；The additive amount of ethyl acetate is 1.5-2.5 times of organic phase quality.
7. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that the automatic reactor
It being made of several reaction kettles (1), the outlet tube of previous reaction kettle is connect with the inlet tube of the latter reaction kettle, the last one
The outlet tube of reaction kettle is connected with filtering tank (9).
8. the production technology of Novolac Cyanate Ester Resins according to claim 1, which is characterized in that the reaction kettle (1)
Top be equipped with jet chimney (13), jet chimney (13) is connect with main pipeline (14), and one end of main pipeline (14) passes through
First shut-off valve (15), compressor (16) are connect with the inlet end of the second condenser (5), and the other end of main pipeline (14) passes through the
Two shut-off valves (17) are connect with the outlet side of the second condenser (5)；The main pipeline (14), the first shut-off valve (15), compressor
(16), the second condenser (5), the second shut-off valve (17) are interconnected to form high/low temperature steam passage two-by-two.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195511A (en) * | 2020-01-17 | 2020-05-26 | 中国航空工业集团公司济南特种结构研究所 | Environment-friendly synthesis system of cyanate ester resin |
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