CN115093506A - Epoxy resin dechlorinating agent, preparation method thereof and method for preparing low-chlorine epoxy resin by using epoxy resin dechlorinating agent - Google Patents
Epoxy resin dechlorinating agent, preparation method thereof and method for preparing low-chlorine epoxy resin by using epoxy resin dechlorinating agent Download PDFInfo
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- CN115093506A CN115093506A CN202210862792.8A CN202210862792A CN115093506A CN 115093506 A CN115093506 A CN 115093506A CN 202210862792 A CN202210862792 A CN 202210862792A CN 115093506 A CN115093506 A CN 115093506A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 193
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 193
- 239000000460 chlorine Substances 0.000 title claims abstract description 96
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 89
- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 239000012043 crude product Substances 0.000 claims abstract description 35
- 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 abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 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
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 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
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 13
- 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
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000006298 dechlorination reaction Methods 0.000 claims description 10
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- UXRJVATUESCPLY-UHFFFAOYSA-N 4-ethenyloxolan-2-ol Chemical compound OC1CC(C=C)CO1 UXRJVATUESCPLY-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003828 vacuum filtration Methods 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
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001228 spectrum Methods 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
- 238000011161 development Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 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
- 230000004075 alteration Effects 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
- 125000001309 chloro group Chemical group Cl* 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
- 230000000694 effects 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002516 radical scavenger 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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 relates to the technical field of epoxy resin, in particular to an epoxy resin dechlorinating agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the epoxy resin dechlorinating agent, and can solve the problem of high hydrolytic chlorine content in the epoxy resin to a certain extent. The preparation method of the epoxy resin dechlorinating agent comprises the following steps: dropwise adding sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution; dropwise adding azodiisobutyronitrile into the first reaction liquid under a first preset condition, and continuing stirring for 2-3 h to obtain a first crude product; filtering the first crude product to remove impurities to obtain a filtrate; cooling the filtrate to below 60 ℃, and performing reduced pressure suction filtration to obtain a precipitated solid; the operations of washing and filtering the precipitated solid by toluene are repeated for at least three times to obtain a product after impurity removal; and drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
Description
Technical Field
The application relates to the technical field of epoxy resin, in particular to an epoxy resin dechlorinating agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the epoxy resin dechlorinating agent.
Background
In recent years, with the rise of internet of things, big data, artificial intelligence and 5G technologies, the performance of electronic and electrical products is continuously improved due to the requirements of more complex and diversified functions, larger information load capacity and faster conduction rate.
The epoxy resin, a key material for packaging, bonding and fixing electronic components, hinders the development of electronic and electrical 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. Therefore, the removal of hydrolytic chlorine has become one of the key steps in the development of epoxy resin materials.
The method for removing the hydrolysis chlorine comprises the following steps: 1, 2-chlorohydrin ether is cyclized as much as possible by adding NaOH or a phase transfer catalyst in the synthesis process of the resin, but the complexity of the preparation process is increased; the method also comprises the step of refining the epoxy resin by a vacuum molecular distillation method, a solvent extraction method, a crystallization separation method and the like at the later stage, but the method has high cost, complex process and high energy consumption, and limits the application of the method 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 dechlorinating agent, a preparation method thereof and a method for preparing low-chlorine epoxy resin by using the epoxy resin dechlorinating agent.
The embodiment of the application is realized as follows:
the embodiment of the application provides an epoxy resin dechlorination agent, the structural formula of the epoxy resin dechlorination agent is as follows:
wherein a, b and c are polymerization degrees, 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.
Another embodiment of the present application provides a method for preparing an epoxy resin dechlorinating agent, comprising the following steps:
dropwise adding sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution;
dropwise adding azodiisobutyronitrile into the first reaction liquid under a first preset condition, and continuing stirring for 2-3 h to obtain a first crude product;
filtering and removing impurities from the first crude product to obtain a filtrate;
cooling the filtrate to below 60 ℃, and performing reduced pressure suction filtration to obtain a precipitated solid;
repeating the operations of washing and filtering the precipitated solid by using toluene for at least three times to obtain a product after impurity removal;
and drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
In some embodiments, the first preset condition comprises: 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-vinyltetrahydro-2-pyran-2-ol are reacted under the initiation of azobisisobutyronitrile to form the polar adsorbent for chlorine removal of epoxy resin according to the following reaction principle:
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 the cyclic hemiacetal to the toluene is 1: 4 to 8.
In some embodiments, the azobisisobutyronitrile is added in an amount of 0.5% to 0.6% by mass of the total mass of the sodium allylsulfonate, the styrene, and the cyclic hemiacetal containing vinyl monomer.
Another embodiment of the present disclosure provides a method for preparing a low-chlorine epoxy resin using an epoxy resin dechlorinating agent, including the steps of:
under a third preset condition, performing aldol condensation reaction on the epoxy resin dechlorinating 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 the hydrolytic chlorine and the epoxy resin dechlorinating agent and unreacted epoxy resin not containing the 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 comprises a reaction temperature of 140 to 160 ℃ and a reaction time of 1 to 4 hours;
subjecting the second crude product to a filtration separation, further comprising:
and filtering and separating the second crude product when the temperature of the second crude product is 140-160 ℃.
In some embodiments, the reaction principle of the reaction of the epoxy resin dechlorination agent and the epoxy resin containing hydrolyzed chlorine is as follows:
the beneficial effect of this application: firstly, sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal are polymerized to prepare epoxy resin dechlorinating agent, then the cyclic hemiacetal group in the epoxy resin dechlorinating agent is easy to react with the hydroxyl on the adjacent carbon of the hydrolytic chlorine in the epoxy resin to form stable acetal polymer, finally the stable acetal polymer is filtered when the epoxy resin dechlorinating agent is hot, and the epoxy resin which does not participate in the reaction and does not contain the hydrolytic chlorine is separated from polymer particles to obtain the low-chlorine epoxy resin. The chlorine content of the low-chlorine epoxy resin prepared by the epoxy resin dechlorinating agent is lower than 300 ppm.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a nuclear magnetic hydrogen spectrum of an epoxy resin dechlorinating agent provided in an embodiment of the present application.
Detailed Description
To make the objects, embodiments and advantages of the present application clearer, the following description of exemplary embodiments of the present application will clearly and completely describe the exemplary embodiments of the present application with reference to the accompanying drawings in the exemplary embodiments of the present application, and it is to be understood that the described exemplary embodiments are only a part of the embodiments of the present application, and not all of the embodiments.
It should be noted that the brief descriptions of the terms in the present application are only for the convenience of understanding the embodiments described below, and are not intended to limit the embodiments of the present application. These terms should be understood in their ordinary and customary meaning unless otherwise indicated.
The technical solutions provided in the present application are explained in detail below with reference to specific examples.
FIG. 1 shows a nuclear magnetic hydrogen spectrum of an epoxy resin dechlorinating agent provided by an embodiment of the present application.
The method aims to remove the hydrolytic chlorine in the epoxy resin, reduce the content of chlorine impurities in the epoxy resin and further reduce the corrosion of HCl generated by the reaction of the chlorine-containing impurities and water on a circuit board.
The application prepares the epoxy resin dechlorinating agent by polymerizing sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal, and the reaction principle is as follows:
FIG. 1 is a nuclear magnetic hydrogen spectrum of an epoxy resin chlorine scavenger, wherein it can be seen that the peak a is 1.3; δ 1.13 is the peak of b; δ is a peak of c at 3.08 and 2.83; δ 1.83 is the peak of d; a peak at δ — 2.58 for e; peak with δ being 7.32 and f; peak at δ 1.13 is g; a peak for h, δ 1.00; δ 1.50 is the peak of i; a peak with δ ═ 5.70 of j; a peak with k being 4.32; a peak of δ — 0.70 for l; a peak with δ ═ 1.29 of m; a peak with δ — 3.64 being n; δ — 3.35 is the peak of o; the peak of p is δ 4.63.
The structure of the epoxy resin dechlorinating agent comprises a sodium sulfonate group, a benzene ring and a cyclic hemiacetal group.
The purpose of introducing sodium allylsulfonate into the epoxy resin dechlorinating agent is to enable the epoxy resin dechlorinating agent to have the performance of an ionic surfactant, and the epoxy resin dechlorinating agent has the characteristic of fast crystallization by utilizing the characteristics that the solubility of the ionic surfactant is increased above the Krafft point (60 ℃) and is reduced below the Krafft point (60 ℃), so that the epoxy resin dechlorinating agent can be separated from the unreacted reactant.
Further, since the viscosity of the epoxy resin decreases with increasing temperature, the epoxy resin is in a flowable solution state (as "wet" in separation) when the temperature is increased above 140 ℃. The rigidity of the epoxy resin dechlorinating agent can be improved due to the introduction of a large number of benzene ring structures in the prepared epoxy resin dechlorinating agent, the crystallinity and the melting point of a polymer obtained by the reaction of the epoxy resin containing the hydrolyzed chlorine and the epoxy resin dechlorinating agent are higher (dry in separation), and the polymer and the low-chlorine epoxy resin containing the epoxy resin without the hydrolyzed chlorine are further favorably separated 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 the reaction.
The principle of the reaction between the epoxy resin containing the hydrolytic chlorine and the epoxy resin dechlorinating agent is as follows: since the hydrolyzed chlorine in the epoxy resin is located at the terminal group, the hydroxyl group on the carbon adjacent to the terminal chlorine has better activity. Therefore, the cyclic hemiacetal group in the epoxy resin dechlorinating 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 one
The preparation method of the epoxy resin dechlorinating agent comprises the following steps:
204.0g of toluene was added to the three-necked flask, and the stirring was turned on.
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, warmed to 80 ℃ and stirred for 1 hour.
255mg of Azobisisobutyronitrile (AIBN) was added to the three-necked flask, and after stirring and reacting for 2 hours, the reaction was terminated to obtain a first crude product.
And filtering the prepared first crude product while the first crude product is hot to remove impurities, cooling the filtrate to room temperature to precipitate a solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the step for 3 times to obtain the product after impurity removal.
And drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
The method for preparing the low-chlorine epoxy resin by using the epoxy resin dechlorinating agent comprises the following steps:
the epoxy resin dechlorinating agent is put into epoxy resin and heated to 140 ℃, hydroxyl in the epoxy resin dechlorinating agent and hydroxyl in the epoxy resin containing the hydrolyzed chlorine impurities react for 1 hour to ensure that the epoxy resin containing the hydrolyzed chlorine is grafted on the epoxy resin dechlorinating agent to generate polymer particles, then the polymer particles are filtered when the polymer particles are hot, and the epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine is separated from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content of the epoxy resin before and after dechlorination was measured.
Example two
The preparation method of the epoxy resin dechlorinating agent comprises the following steps:
463.2g of toluene were added to the three-necked flask, and the stirring was turned on.
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, warmed to 80 ℃ and stirred for 1 hour.
386mg of Azobisisobutyronitrile (AIBN) is added into the three-neck flask, and after continuous stirring and reaction for 2 hours, the reaction is finished to obtain a first crude product.
And filtering the prepared first crude product while the first crude product is hot to remove impurities, cooling the filtrate to room temperature to precipitate a solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the step for 3 times to obtain the product after impurity removal.
And drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
The method for preparing the low-chlorine epoxy resin by using the epoxy resin dechlorinating agent comprises the following steps:
and (2) putting the epoxy resin dechlorinating agent into epoxy resin, heating to 150 ℃, reacting hydroxyl in the epoxy resin dechlorinating agent with hydroxyl in the epoxy resin containing the hydrolyzed chlorine impurities for 2 hours to ensure that the epoxy resin containing the hydrolyzed chlorine is grafted to the epoxy resin dechlorinating agent to generate polymer particles, filtering while hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content of the epoxy resin before and after dechlorination was measured.
EXAMPLE III
The preparation method of the epoxy resin dechlorinating agent comprises the following steps:
408.0g of toluene were added to a three-necked flask, and stirring was turned on.
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, warmed to 80 ℃ and stirred for 1 hour.
255mg of Azobisisobutyronitrile (AIBN) was added to the three-necked flask, and after stirring and reaction for 2 hours, the reaction was terminated to obtain a first crude product.
And filtering the prepared first crude product while the first crude product is hot to remove impurities, cooling the filtrate to room temperature to precipitate a solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the step for 3 times to obtain the product after impurity removal.
And drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
The method for preparing the low-chlorine epoxy resin by using the epoxy resin dechlorinating agent comprises the following steps:
and (2) putting the epoxy resin dechlorinating agent into epoxy resin, heating to 150 ℃, reacting hydroxyl in the epoxy resin dechlorinating agent with hydroxyl in the epoxy resin containing the hydrolyzed chlorine impurities for 3 hours to ensure that the epoxy resin containing the hydrolyzed chlorine is grafted on the epoxy resin dechlorinating agent to generate polymer particles, filtering while the mixture is hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content of the epoxy resin before and after dechlorination was measured.
Example four
The preparation method of the epoxy resin dechlorinating agent comprises the following steps:
the preparation method of the epoxy resin dechlorinating agent comprises the following steps:
620.4g of toluene were added to a three-necked flask, and stirring was turned on.
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, warmed to 80 ℃ and stirred for 2 hours.
517mg of Azobisisobutyronitrile (AIBN) was added to the three-necked flask, and after stirring and reaction for 2 hours, the reaction was terminated to obtain a first crude product.
And filtering the prepared first crude product while the first crude product is hot to remove impurities, cooling the filtrate to room temperature to precipitate a solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the step for 3 times to obtain the product after impurity removal.
And drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
The method for preparing the low-chlorine epoxy resin by using the epoxy resin dechlorinating agent comprises the following steps:
and (2) putting the epoxy resin dechlorinating agent into epoxy resin, heating to 160 ℃, reacting hydroxyl in the epoxy resin dechlorinating agent with hydroxyl in the epoxy resin containing the hydrolyzed chlorine impurities for 4 hours to ensure that the epoxy resin containing the hydrolyzed chlorine is grafted to the epoxy resin dechlorinating agent to generate polymer particles, filtering while hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content of the epoxy resin before and after dechlorination was measured.
EXAMPLE five
The preparation method of the epoxy resin dechlorinating agent comprises the following steps:
517.4g of toluene were added to a three-necked flask, and stirring was turned on.
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, warmed to 80 ℃ and stirred for 1 hour.
648mg of Azobisisobutyronitrile (AIBN) was added to the three-necked flask and after 2 hours of continuous stirring and reaction, the reaction was terminated to obtain a first crude product.
And filtering the prepared first crude product while the first crude product is hot to remove impurities, cooling the filtrate to room temperature to precipitate a solid, and carrying out vacuum filtration.
Dissolving the precipitated solid in toluene, heating to 90 ℃, filtering again, and repeating the step for 3 times to obtain the product after impurity removal.
And drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
The method for preparing the low-chlorine epoxy resin by using the epoxy resin dechlorinating agent comprises the following steps of:
and (2) putting the epoxy resin dechlorinating agent into epoxy resin, heating to 160 ℃, reacting hydroxyl in the epoxy resin dechlorinating agent with hydroxyl in the epoxy resin containing the hydrolyzed chlorine impurities for 2 hours to ensure that the epoxy resin containing the hydrolyzed chlorine is grafted to the epoxy resin dechlorinating agent to generate polymer particles, filtering while hot, and separating the epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine from the polymer particles to obtain the low-chlorine epoxy resin.
The chlorine content of the epoxy resin before and after dechlorination was measured.
The results of the measurement of the chlorine content of the epoxy resin before impurity removal and the chlorine content of the epoxy resin after impurity removal in examples 1 to 5 by the Mohr method are shown in Table 1.
As can be seen from Table 1, the method for preparing the ultra-pure epoxy resin by using the epoxy resin dechlorinating agent can effectively remove the epoxy resin containing the hydrolyzed chlorine and reduce the chlorine content of the epoxy resin.
Wherein, when the molar 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 dechlorinating agent is optimal. When the epoxy resin dechlorinating agent reacts with the epoxy resin containing hydrolytic chlorine at the temperature of 150 ℃ for 2 hours, the dechlorinating effect is best. The low-chlorine epoxy resin prepared by the method can be applied to the field of electronics.
TABLE 1 test results of chlorine content of epoxy resin in examples 1 to 5
| Examples | Epoxy resin chlorine content/ppm before impurity removal | Chlorine content/ppm of epoxy resin after |
| 1 | 1175 | 241 |
| 2 | 1208 | 229 |
| 3 | 1237 | 294 |
| 4 | 1184 | 278 |
| 5 | 1174 | 281 |
According to the method, firstly sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal are polymerized to prepare the epoxy resin dechlorinating agent, then the cyclic hemiacetal group in the epoxy resin dechlorinating agent is easy to react with hydroxyl on adjacent carbon of hydrolyzed chlorine in the epoxy resin to form a stable acetal polymer, and finally the stable acetal polymer is filtered when the epoxy resin dechlorinating agent is hot, and epoxy resin which does not participate in the reaction and does not contain the hydrolyzed chlorine is separated from polymer particles to obtain the low-chlorine epoxy resin. The chlorine content of the low-chlorine epoxy resin prepared by the epoxy resin dechlorinating agent is lower than 300 ppm.
The removing mechanism of the chlorine impurities in the epoxy resin is clear, 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 more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The epoxy resin dechlorination agent is characterized in that the structural formula of the epoxy resin dechlorination agent is as follows:
wherein a, b and c are polymerization degrees, 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 dechlorinating agent of claim 1, comprising the following steps:
dropwise adding sodium allylsulfonate, styrene and vinyl monomer containing cyclic hemiacetal into a reactor filled with toluene solution to obtain a first reaction solution;
dropwise adding azodiisobutyronitrile into the first reaction solution under a first preset condition, and then continuously stirring for 2-3 h to obtain a first crude product;
filtering and removing impurities from the first crude product to obtain a filtrate;
cooling the filtrate to below 60 ℃, and performing reduced pressure suction filtration to obtain a precipitated solid;
repeating the operations of washing and filtering the precipitated solid by using toluene for at least three times to obtain a product after impurity removal;
and drying the product after impurity removal to prepare the epoxy resin dechlorinating agent.
3. The method for preparing epoxy resin chlorine remover according to claim 2, wherein the first preset condition comprises: the reaction temperature is 80-100 ℃.
4. The method for preparing epoxy resin dechlorinating agent according to claim 2, wherein 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.
5. The method for preparing an epoxy resin dechlorinating agent according to claim 4,
the sodium allylsulfonate, the styrene and the 4-methyl-4-vinyl tetrahydro-2-pyran-2-ol are initiated to react under the initiation of the azodiisobutyronitrile to generate the polar adsorbent for removing chlorine of the epoxy resin, and the reaction principle is as follows:
6. the method for preparing epoxy resin dechlorinating agent according to claim 2, wherein the molar ratio of the sodium allylsulfonate, the styrene and the 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 the cyclic hemiacetal to the toluene is 1: 4 to 8.
7. The method for preparing the epoxy resin dechlorinating agent according to claim 2, wherein the azobisisobutyronitrile is added in an amount of 0.5 to 0.6% based on the total mass of the sodium allylsulfonate, the styrene and the cyclic hemiacetal containing vinyl monomer.
8. A method for preparing low-chlorine epoxy resin by using an epoxy resin dechlorinating agent is characterized by comprising the following steps:
under a third preset condition, performing aldol condensation reaction on the epoxy resin dechlorinating 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 the hydrolytic chlorine and the epoxy resin dechlorinating agent and unreacted epoxy resin not containing the 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 epoxy resin dechlorinating agent according to claim 8, wherein the third preset condition comprises that the reaction temperature is 140-160 ℃ and the reaction time is 1-4 h;
subjecting the second crude product to a filtration separation, further comprising:
and filtering and separating the second crude product when the temperature of the second crude product is 140-160 ℃.
10. The method for preparing a low-chlorine epoxy resin by using an epoxy resin dechlorinating agent according to claim 8, wherein the reaction principle of the reaction of the epoxy resin dechlorinating agent and the epoxy resin containing hydrolyzed chlorine is as follows:
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| 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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| 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 |
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