CN115093506B - Epoxy resin chlorine removing agent, preparation method thereof and method for preparing low-chlorine epoxy resin by using epoxy resin chlorine removing agent - Google Patents
Epoxy resin chlorine removing agent, preparation method thereof and method for preparing low-chlorine epoxy resin by using epoxy resin chlorine removing agent Download PDFInfo
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- CN115093506B CN115093506B CN202210862792.8A CN202210862792A CN115093506B CN 115093506 B CN115093506 B CN 115093506B CN 202210862792 A CN202210862792 A CN 202210862792A CN 115093506 B CN115093506 B CN 115093506B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 194
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 194
- 239000000460 chlorine Substances 0.000 title claims abstract description 185
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 185
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000012043 crude product Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 29
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- -1 cyclic hemiacetal Chemical class 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000002516 radical scavenger Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000005882 aldol condensation reaction Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000001976 hemiacetal group Chemical group 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- UXRJVATUESCPLY-UHFFFAOYSA-N 4-ethenyloxolan-2-ol Chemical compound OC1CC(C=C)CO1 UXRJVATUESCPLY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application belongs to the technical field of epoxy resin, and particularly relates to an epoxy resin chlorine removing agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the epoxy resin chlorine removing agent, which can solve the problem of high content of hydrolytic chlorine in the epoxy resin to a certain extent. The preparation method of the epoxy resin chlorine removal agent comprises the following steps: dropwise adding sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution; under a first preset condition, adding azo diiso Ding Qingdi to the first reaction liquid, and continuing stirring for 2-3 hours to obtain a first crude product; filtering and removing impurities from the first crude product to obtain filtrate; cooling the filtrate to below 60 ℃, and performing vacuum filtration to obtain precipitated solids; repeating the operation of washing and filtering the precipitated solid by toluene for at least three times to obtain a product after impurity removal; and drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
Description
Technical Field
The application relates to the technical field of epoxy resin, in particular to an epoxy resin chlorine removing agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the same.
Background
In recent years, with the rise of the internet of things, big data, artificial intelligence and 5G technology, the performance of electronic and electric products is continuously improved due to more complex and multiple functions, larger information load and faster conduction rate requirements.
The epoxy resin, which is a key material for packaging, bonding and fixing electronic components, is prevented from developing electronic and electric products due to the existence of hydrolytic chlorine, and particularly, the hydrolytic chlorine in the epoxy resin corrodes a circuit board due to HCl generated by hydrolysis. Thus, the removal of the hydrolytic chlorine has become one of the key steps in the development of epoxy materials.
The method for removing the hydrolytic chlorine comprises the following steps: cyclizing the 1, 2-chlorohydrin ether as much as possible by adding NaOH or a phase transfer catalyst during the synthesis of the resin, but increasing the complexity of the preparation process; the method also comprises the steps of refining the epoxy resin by a vacuum molecular distillation method, a solvent extraction method, a crystallization separation method and the like in the later stage, but has high cost, complex process and high energy consumption, and limits the application of the epoxy resin in industrial production.
Disclosure of Invention
In order to solve the problem of high content of organic chlorine in epoxy resin, the application provides an epoxy resin chlorine removing agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the same.
Embodiments of the present application are implemented as follows:
the embodiment of the application provides an epoxy resin chlorine removal agent, which has the following structural formula:
wherein a, b and c are polymerization degree, the value range of a is 500-1000, the value range of b is 500-1000, and the value range of c is 500-2000.
The application also provides a preparation method of the epoxy resin chlorine removal agent, which comprises the following steps:
dropwise adding sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution;
under a first preset condition, adding azo diiso Ding Qingdi to the first reaction liquid, and continuing stirring for 2-3 hours to obtain a first crude product;
filtering and removing impurities from the first crude product to obtain filtrate;
cooling the filtrate to below 60 ℃, and performing vacuum filtration to obtain precipitated solids;
repeating the operation of washing and filtering the precipitated solid by toluene for at least three times to obtain a product after impurity removal;
and drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
In some embodiments, the first preset condition includes: the reaction temperature is 80-100 ℃.
In some embodiments, the cyclic hemiacetal-containing vinyl monomer is one of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol, 4-methyl-4-vinyltetrahydro-2-pyran-2-ol, or 4-vinyltetrahydrofuran-2-ol.
In some embodiments, the sodium allylsulfonate, styrene and 4-methyl-4-vinyl tetrahydro-2-pyran-2-ol react under the initiation of azobisisobutyronitrile to form the polar adsorbent for removing chlorine from epoxy resin, and the reaction principle is as follows:
in some embodiments, the molar ratio of sodium allylsulfonate, styrene, and cyclic hemiacetal-containing vinyl monomer is 1:1: 1-4, wherein the mass ratio of the total mass of the sodium allylsulfonate, the styrene and the vinyl monomer containing cyclic hemiacetal to toluene is 1:4 to 8.
In some embodiments, the azobisisobutyronitrile is added in an amount of 0.5% to 0.6% of the total mass of sodium allylsulfonate, styrene, and cyclic hemi-acetal containing vinyl monomer.
In another embodiment of the present application, a method for preparing a low-chlorine epoxy resin using an epoxy resin chlorine scavenger is provided, comprising the steps of:
under a third preset condition, performing aldol condensation reaction on the epoxy resin chlorine removal agent and the epoxy resin to obtain a second crude product, wherein the second crude product liquid comprises a polymer formed by combining the epoxy resin containing hydrolytic chlorine and the epoxy resin chlorine removal agent and the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine;
and filtering and separating the second crude product, and removing the polymer in the second crude product to obtain the low-chlorine epoxy resin, wherein the chlorine content of the low-chlorine epoxy resin is lower than that of the epoxy resin before reaction.
In some embodiments, the third preset condition includes a reaction temperature of 140-160 ℃ and a reaction time of 1-4 hours;
filtering the second crude product, further comprising:
and filtering and separating the second crude product at the temperature of 140-160 ℃.
In some embodiments, the reaction principle of the epoxy resin chlorine scavenger reacting with the epoxy resin containing the hydrolytic chlorine is:
the application has the beneficial effects that: firstly, preparing an epoxy resin chlorine removing agent by polymerizing sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal, then enabling the cyclic hemiacetal group in the epoxy resin chlorine removing agent to easily react with hydroxyl groups on adjacent carbon of hydrolytic chlorine in the epoxy resin to form a stable acetal polymer, and finally filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolytic chlorine from polymer particles to obtain the low-chlorine epoxy resin. The chlorine content of the low-chlorine epoxy resin prepared by using the epoxy resin chlorine remover is lower than 300ppm.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of an epoxy resin chlorine removal agent provided by an embodiment of the application.
Detailed Description
For the purposes of making the objects, embodiments and advantages of the present application more apparent, an exemplary embodiment of the present application will be described more fully hereinafter with reference to the accompanying drawings in which exemplary embodiments of the application are shown, it being understood that the exemplary embodiments described are merely some, but not all, of the examples of the application.
It should be noted that the brief description of the terminology in the present application is for the purpose of facilitating understanding of the embodiments described below only and is not intended to limit the embodiments of the present application. Unless otherwise indicated, these terms should be construed in their ordinary and customary meaning.
The technical scheme provided by the application is explained in detail below with reference to specific embodiments.
FIG. 1 shows a nuclear magnetic hydrogen spectrum of an epoxy resin chlorine removal agent provided by an embodiment of the application.
The application aims to remove hydrolytic chlorine in epoxy resin, reduce the content of chlorine impurities in the epoxy resin, and further reduce corrosion of HCl generated by the reaction of chlorine impurities and water on a circuit board.
The application firstly prepares an epoxy resin chlorine removal agent by polymerizing sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal, and the reaction principle is as follows:
fig. 1 is a nuclear magnetic resonance spectrum of an epoxy resin chlorine scavenger, and as can be seen from the figure, δ=1.3 is a peak of a; δ=1.13 is the peak of b; delta = 3.08, 2.83 is the peak of c; δ=1.83 is the peak of d; δ=2.58 is the peak of e; δ=7.32 is the peak of f; δ=1.13 is the peak of g; δ=1.00 is the peak of h; δ=1.50 is the peak of i; δ=5.70 is the peak of j; δ=4.32 is the peak of k; delta = 0.70 is peak of l; δ=1.29 is the peak of m; δ=3.64 is the peak of n; delta = 3.35 is a peak of o; δ=4.63 is the peak of p.
The structure of the epoxy resin chlorine remover comprises sodium sulfonate groups, benzene rings and cyclic hemiacetal groups.
The purpose of introducing sodium allylsulfonate into the epoxy resin chlorine removal agent is to enable the epoxy resin chlorine removal agent to have the performance of an ionic surfactant, and the characteristic that the solubility of the ionic surfactant is increased above a Krafft point (60 ℃) and is reduced below the Krafft point (60 ℃) is utilized to enable the epoxy resin chlorine removal agent to have the characteristic of quick crystallization, so that the epoxy resin chlorine removal agent can be separated from unreacted reactants.
Further, since the viscosity of the epoxy resin decreases with increasing temperature, the epoxy resin is in a flowable solution state (being "wet" in separation) when the temperature increases above 140 ℃. The prepared epoxy resin chlorine removing agent has the advantages that a large amount of benzene ring structures are introduced, so that the rigidity of the epoxy resin chlorine removing agent can be improved, the crystallinity and the melting point (which are dry in separation) of a polymer obtained by the reaction of the epoxy resin containing hydrolytic chlorine and the epoxy resin chlorine removing agent are higher, and the separation of the polymer and the low-chlorine epoxy resin containing the epoxy resin without hydrolytic chlorine is facilitated, so that the low-chlorine epoxy resin is obtained, and the chlorine content of the low-chlorine epoxy resin is lower than that of the epoxy resin before the reaction.
The principle of the reaction of the epoxy resin containing the hydrolytic chlorine and the epoxy resin chlorine removing agent is as follows: since the hydrolytic chlorine in the epoxy resin is positioned at the end group, the hydroxyl on the carbon adjacent to the end group chlorine has better activity. Thus, the cyclic hemiacetal group in the epoxy resin chlorine removal agent is easy to react with the hydroxyl group on the adjacent carbon of the hydrolyzed chlorine in the epoxy resin to form a stable acetal substance, and the principle is as follows:
example 1
The preparation method of the epoxy resin chlorine removal agent comprises the following steps:
204.0g of toluene was added to the three-necked flask, and stirring was started.
14.4g of sodium allylsulfonate 10.4g of styrene and 26.2g of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol were added to a three-necked flask with stirring, heated to 80℃and stirred for 1h.
255mg of Azobisisobutyronitrile (AIBN) was added to the above three-necked flask, and after continuing stirring and reacting for 2 hours, the reaction was completed to obtain a first crude product.
Filtering the prepared first crude product while the first crude product is hot, removing impurities, cooling the filtrate to room temperature, precipitating solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the steps for 3 times to obtain the product after impurity removal.
And drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
A method for preparing a low chlorine epoxy resin using an epoxy resin chlorine scavenger comprising the steps of:
and (3) placing the epoxy resin chlorine removing agent into epoxy resin, heating to 140 ℃, reacting hydroxyl in the epoxy resin chlorine removing agent with hydroxyl in the epoxy resin containing hydrolytic chlorine impurities for 1h, grafting the epoxy resin containing hydrolytic chlorine onto the epoxy resin chlorine removing agent to generate polymer particles, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content in the epoxy resin before and after chlorine removal was measured.
Example two
The preparation method of the epoxy resin chlorine removal agent comprises the following steps:
463.2g of toluene were added to the three-necked flask and stirring was started.
14.4g of sodium allylsulfonate 10.4g of styrene and 52.4g of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol were added to a three-necked flask with stirring, heated to 80℃and stirred for 1h.
386mg of Azobisisobutyronitrile (AIBN) was added to the above three-necked flask, and after continuously stirring and reacting for 2 hours, the reaction was completed to obtain a first crude product.
Filtering the prepared first crude product while the first crude product is hot, removing impurities, cooling the filtrate to room temperature, precipitating solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the steps for 3 times to obtain the product after impurity removal.
And drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
A method for preparing a low chlorine epoxy resin using an epoxy resin chlorine scavenger comprising the steps of:
and (3) placing the epoxy resin chlorine removing agent into epoxy resin, heating to 150 ℃, reacting hydroxyl in the epoxy resin chlorine removing agent with hydroxyl in the epoxy resin containing hydrolytic chlorine impurities for 2 hours, grafting the epoxy resin containing hydrolytic chlorine onto the epoxy resin chlorine removing agent to generate polymer particles, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content in the epoxy resin before and after chlorine removal was measured.
Example III
The preparation method of the epoxy resin chlorine removal agent comprises the following steps:
408.0g of toluene was added to a three-necked flask, and stirring was started.
14.4g of sodium allylsulfonate 10.4g of styrene and 26.2g of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol were added to a three-necked flask with stirring, heated to 80℃and stirred for 1h.
255mg of Azobisisobutyronitrile (AIBN) was added to the above three-necked flask, and after continuing stirring and reacting for 2 hours, the reaction was completed to obtain a first crude product.
Filtering the prepared first crude product while the first crude product is hot, removing impurities, cooling the filtrate to room temperature, precipitating solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the steps for 3 times to obtain the product after impurity removal.
And drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
A method for preparing a low chlorine epoxy resin using an epoxy resin chlorine scavenger comprising the steps of:
and (3) placing the epoxy resin chlorine removing agent into epoxy resin, heating to 150 ℃, reacting hydroxyl in the epoxy resin chlorine removing agent with hydroxyl in the epoxy resin containing hydrolytic chlorine impurities for 3 hours, grafting the epoxy resin containing hydrolytic chlorine onto the epoxy resin chlorine removing agent to generate polymer particles, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content in the epoxy resin before and after chlorine removal was measured.
Example IV
The preparation method of the epoxy resin chlorine removal agent comprises the following steps:
the preparation method of the epoxy resin chlorine removal agent comprises the following steps:
620.4g of toluene was added to a three-necked flask, and stirring was started.
14.4g of sodium allylsulfonate 10.4g of styrene and 78.6g of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol were added to a three-necked flask with stirring, heated to 80℃and stirred for 2h.
517mg of Azobisisobutyronitrile (AIBN) was added to the above three-necked flask, and after continuously stirring and reacting for 2 hours, the reaction was completed to obtain a first crude product.
Filtering the prepared first crude product while the first crude product is hot, removing impurities, cooling the filtrate to room temperature, precipitating solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the steps for 3 times to obtain the product after impurity removal.
And drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
A method for preparing a low chlorine epoxy resin using an epoxy resin chlorine scavenger comprising the steps of:
and (3) placing the epoxy resin chlorine removing agent into epoxy resin, heating to 160 ℃, reacting hydroxyl in the epoxy resin chlorine removing agent with hydroxyl in the epoxy resin containing hydrolytic chlorine impurities for 4 hours, grafting the epoxy resin containing hydrolytic chlorine onto the epoxy resin chlorine removing agent to generate polymer particles, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content in the epoxy resin before and after chlorine removal was measured.
Example five
The preparation method of the epoxy resin chlorine removal agent comprises the following steps:
517.4g of toluene was added to a three-necked flask, and stirring was started.
14.4g of sodium allylsulfonate 10.4g of styrene and 104.8g of 6- [ (benzyloxy) methyl ] -4-vinyl-4-methyloxa-2-ol were added to a three-necked flask with stirring, heated to 80℃and stirred for 1h.
648mg of Azobisisobutyronitrile (AIBN) was added to the above-mentioned three-necked flask, and after stirring and reacting for 2 hours, the reaction was completed to obtain a first crude product.
Filtering the prepared first crude product while the first crude product is hot, removing impurities, cooling the filtrate to room temperature, precipitating solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the steps for 3 times to obtain the product after impurity removal.
And drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
A method for preparing a low chlorine epoxy resin using an epoxy resin chlorine scavenger comprising the steps of:
and (3) placing the epoxy resin chlorine removing agent into epoxy resin, heating to 160 ℃, reacting hydroxyl in the epoxy resin chlorine removing agent with hydroxyl in the epoxy resin containing hydrolytic chlorine impurities for 2 hours, grafting the epoxy resin containing hydrolytic chlorine onto the epoxy resin chlorine removing agent to generate polymer particles, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content in the epoxy resin before and after chlorine removal was measured.
The chlorine content of the epoxy resin before the removal of the impurities and the chlorine content of the epoxy resin after the removal of the impurities in examples 1 to 5 were measured by the Morse method, and the results are shown in Table 1.
As can be seen from Table 1, the method for preparing ultra-high purity epoxy resin by using the epoxy resin chlorine scavenger of the present application can effectively remove the epoxy resin containing the hydrolytic chlorine, and reduce the chlorine content of the epoxy resin.
Wherein, when the mol ratio of the styrene to the vinyl monomer containing the cyclic hemiacetal is 1:2, the mass ratio of the monomer to the toluene is 1:6, the reaction temperature is 70 ℃, and the reaction time is 2 hours, the performance of the prepared epoxy resin chlorine removal agent is optimal. When the epoxy resin chlorine removing agent reacts with the epoxy resin containing the hydrolytic chlorine for 2 hours at 150 ℃, the chlorine removing effect is best. The low-chlorine epoxy resin prepared by the application can be applied to the field of electronics.
TABLE 1 results of the chlorine content test of epoxy resins in examples 1 to 5
| Examples | Chlorine content/ppm of epoxy resin before impurity removal | Chlorine content/ppm of epoxy resin after impurity removal |
| 1 | 1175 | 241 |
| 2 | 1208 | 229 |
| 3 | 1237 | 294 |
| 4 | 1184 | 278 |
| 5 | 1174 | 281 |
The method comprises the steps of preparing an epoxy resin chlorine removing agent by polymerizing sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal, enabling the cyclic hemiacetal group in the epoxy resin chlorine removing agent to easily react with hydroxyl groups on adjacent carbon of hydrolytic chlorine in the epoxy resin to form a stable acetal polymer, filtering while the epoxy resin is hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolytic chlorine from polymer particles to obtain the low-chlorine epoxy resin. The chlorine content of the low-chlorine epoxy resin prepared by using the epoxy resin chlorine remover is lower than 300ppm.
The removal mechanism of chlorine impurities in the epoxy resin is clear, so that the organic chlorine in the conventional epoxy resin can be effectively removed, and the total chlorine content in the conventional epoxy resin is reduced.
The foregoing is a further elaboration of the present application, and it is not intended that the application be limited to the specific embodiments shown, but rather that a number of simple deductions or substitutions be made by one of ordinary skill in the art without departing from the spirit of the application, all shall be deemed to fall within the scope of the application as defined by the claims which are filed herewith.
Claims (10)
1. The epoxy resin chlorine removing agent is characterized by having the following structural formula:
wherein a, b and c are polymerization degree, the value range of a is 500-1000, the value range of b is 500-1000, and the value range of c is 500-2000.
2. A method for preparing the epoxy resin chlorine removal agent of claim 1, comprising the steps of:
dropwise adding sodium allylsulfonate, styrene and a vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution;
dropwise adding azodiisobutyronitrile to the first reaction liquid under a first preset condition, and then continuing stirring for 2-3 hours to obtain a first crude product;
filtering and removing impurities from the first crude product to obtain filtrate;
cooling the filtrate to below 60 ℃, and performing vacuum filtration to obtain precipitated solids;
repeating the operation of washing and filtering the precipitated solid by toluene for at least three times to obtain a product after impurity removal;
and drying the products after impurity removal to obtain the epoxy resin chlorine removal agent.
3. The method for preparing an epoxy resin chlorine scavenger according to claim 2, wherein the first preset conditions include: the reaction temperature is 80-100 ℃.
4. The method for producing an epoxy resin chlorine scavenger according to claim 2, characterized in that the cyclic hemiacetal-containing vinyl monomer is 4-methyl-4-vinyltetrahydro-2-pyran-2-ol.
5. The method for preparing an epoxy resin chlorine removal agent as defined in claim 4, wherein,
the reaction of sodium allylsulfonate, styrene and 4-methyl-4-vinyl tetrahydro-2-pyran-2-ol under the initiation of azodiisobutyronitrile is carried out to generate the polar adsorbent for removing chlorine from epoxy resin, and the reaction principle is as follows:
6. the method for producing an epoxy resin chlorine scavenger according to claim 2, wherein the molar ratio of sodium allylsulfonate, styrene and a cyclic hemiacetal-containing vinyl monomer is 1:1:1 to 4, and the mass ratio of the total mass of sodium allylsulfonate, styrene and cyclic hemiacetal-containing vinyl monomer to toluene is 1:4 to 8.
7. The method for producing an epoxy resin chlorine scavenger according to claim 2, wherein the azobisisobutyronitrile is added in an amount of 0.5% to 0.6% by mass of the total mass of sodium allylsulfonate, styrene and cyclic hemi-acetal-containing vinyl monomer.
8. A method for preparing low-chlorine epoxy resin by using an epoxy resin chlorine removing agent, which is characterized by comprising the following steps:
under a third preset condition, carrying out aldol condensation reaction on the epoxy resin chlorine removal agent and the epoxy resin to obtain a second crude product, wherein the second crude product liquid comprises a polymer formed by combining the epoxy resin containing hydrolytic chlorine and the epoxy resin chlorine removal agent and the epoxy resin which does not participate in the reaction and does not contain hydrolytic chlorine;
and filtering and separating the second crude product, and removing the polymer in the second crude product to obtain the low-chlorine epoxy resin, wherein the chlorine content of the low-chlorine epoxy resin is lower than that of the epoxy resin before reaction.
9. The method for preparing low-chlorine epoxy resin by using the epoxy resin chlorine removal agent as claimed in claim 8, wherein the third preset condition comprises a reaction temperature of 140-160 ℃ and a reaction time of 1-4 hours;
filtering the second crude product, further comprising:
and filtering and separating the second crude product at the temperature of 140-160 ℃.
10. The method for preparing low-chlorine epoxy resin by using the epoxy resin chlorine removal agent as claimed in claim 8, wherein the reaction principle of the epoxy resin chlorine removal agent and the epoxy resin containing hydrolytic chlorine is as follows:
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| US4017523A (en) * | 1974-05-30 | 1977-04-12 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the continuous preparation of polyglycidyl ethers of polyhydroxy phenols |
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| JPH11349661A (en) * | 1998-06-04 | 1999-12-21 | Sumitomo Chem Co Ltd | Preparation of epoxy resin with low content of hydrolyzable chlorine |
| JP2004211028A (en) * | 2003-01-08 | 2004-07-29 | Toto Kasei Co Ltd | Method for purifying epoxy resin and epoxy resin composition for sealing semiconductor |
| JP2013100385A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| CN113248687A (en) * | 2021-06-23 | 2021-08-13 | 江苏扬农锦湖化工有限公司 | Epoxy resin refining method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017523A (en) * | 1974-05-30 | 1977-04-12 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the continuous preparation of polyglycidyl ethers of polyhydroxy phenols |
| JPH041148A (en) * | 1990-04-17 | 1992-01-06 | Asahi Denka Kogyo Kk | Optically active alkenyl-substituted heptane derivative |
| JPH11349661A (en) * | 1998-06-04 | 1999-12-21 | Sumitomo Chem Co Ltd | Preparation of epoxy resin with low content of hydrolyzable chlorine |
| JP2004211028A (en) * | 2003-01-08 | 2004-07-29 | Toto Kasei Co Ltd | Method for purifying epoxy resin and epoxy resin composition for sealing semiconductor |
| JP2013100385A (en) * | 2011-11-07 | 2013-05-23 | Asahi Kasei E-Materials Corp | Method for producing epoxy resin and epoxy resin obtained using the same |
| CN113248687A (en) * | 2021-06-23 | 2021-08-13 | 江苏扬农锦湖化工有限公司 | Epoxy resin refining method |
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