CN113387806B - Branched compound, preparation method thereof and application thereof in preparing branched alicyclic resin - Google Patents
Branched compound, preparation method thereof and application thereof in preparing branched alicyclic resin Download PDFInfo
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- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/00—Chemical modification by after-treatment
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Abstract
The invention relates to a compound capable of branching, a preparation method thereof and application thereof in preparing branched alicyclic resin. The compound (CTA-Br) with a branched structure has a structure shown as a formula (I): wherein n is an integer between 0 and 3; x 1 、X 2 、X 3 Independently selected from Br or H, and X 1 、X 2 And X 3 At least one of them is Br. The compound contains both a methacrylate structure and a functional group bromine with chain transfer reaction activity, the structure can keep lasting reaction activity, and the structure is copolymerized with a polymer matrix, so that no small molecules are remained in a reaction system in the process of chain transfer reaction. When the branched alicyclic resin is used as a chain transfer agent to react with alicyclic epoxy light-cured resin, the obtained branched alicyclic resin has good curing speed, acid resistance and lower dielectric constant.
Description
Technical Field
The invention belongs to the technical field of photosensitive high polymer materials, and particularly relates to a branched compound, a preparation method thereof and application thereof in preparing branched alicyclic resin.
Background
The main resin in the traditional photocuring solder resist ink is novolac epoxy acrylate resin, has the defects of no high temperature resistance, poor tin resistance, poor acid resistance and the like, has a dielectric constant Dk of approximately 3.8, and is not favorable for being applied to PCB assembly welding ink, three-proofing paint and adhesive in the current rapidly developed 5G communication technology.
The alicyclic epoxy resin has the characteristics of good thermal stability, good weather resistance, excellent electrical insulation (lower dielectric constant) and the like compared with novolac epoxy resin because the epoxy group of the alicyclic epoxy resin is directly connected to the alicyclic ring, a compact rigid molecular structure can be formed, and no benzene ring is contained in the structure, so that the alicyclic epoxy resin is widely used in PCB (printed circuit board) ink, such as typical alicyclic epoxy resin xylonite alicyclic epoxy EPHE3150, and the dielectric constant Dk is approximately equal to 3.5. However, during the curing process, the molecular weight of the resin increases due to the crosslinking action, the viscosity of the system increases, and the curing speed is slow. Therefore, the alicyclic epoxy resin needs to be branched, so that the viscosity of the resin in the curing process can be reduced, the curing reaction is facilitated, and the curing speed is increased; on the other hand, the branched structure can also introduce more activated functional groups and more functional groups, thereby improving the photocuring speed, high temperature resistance, acid resistance and other properties of the resin.
For alicyclic epoxy resin, in the prior art, trimethylolpropane and an epoxy group are subjected to a ring-opening reaction to form branched alicyclic epoxy resin, and then the branched alicyclic epoxy resin is reacted with acrylic acid to generate branched alicyclic epoxy acrylate resin (for example, patent EP1172693A 1), the reaction conditions of the branching mode are harsh, and the branching degree is still to be improved; the alicyclic epoxy resin can be branched by adding a chain transfer agent capable of being branched, but the existing chain transfer agent is usually a RAFT (reversible addition fragmentation chain transfer) agent or a sulfydryl containing dithio ester group, but the RAFT agent has the defects of wide molecular weight distribution and the like, and the sulfydryl and double bonds in the sulfydryl chain transfer agent containing the acrylate group are easy to generate sulfydryl-alkene addition reaction under the condition of light or normal temperature, namely the chain transfer agent has the defect of unstable storage, so that the activity of the branching reaction of a system and the branching degree can be influenced.
In order to improve the curing performance, acid resistance and other performances of the alicyclic epoxy acrylate photocurable resin, a novel branched chain transfer agent with higher reactivity and branching degree needs to be developed.
Disclosure of Invention
The invention aims to overcome the defect of poor chemical tin plating resistance caused by poor acid resistance of the photocuring solder resist ink in the prior art, and provides a novel branched compound with higher reactivity and branching degree, which is used as a chain transfer agent to react with alicyclic epoxy photocuring resin to obtain the branched alicyclic resin with good curing speed, acid resistance and lower dielectric constant.
It is another object of the present invention to provide a process for the preparation of said compounds which can be branched.
It is a further object of the present invention to provide the use of the branching-able compounds for the preparation of branched cycloaliphatic resins.
Another object of the present invention is to provide a method for preparing a branched cycloaliphatic resin.
In order to realize the purpose, the invention adopts the following technical scheme:
a branchable compound (CTA-Br) having a structure according to formula (I):
wherein n is an integer between 0 and 3; x 1 、X 2 、X 3 Independently selected from Br or H, and X 1 、X 2 And X 3 At least one of them is Br.
The compound capable of branching contains methacrylate structure and functional group bromine with chain transfer reaction activity. Specifically, a methacrylate segment is attached to the carboxylic acid end of a fatty acid segment; the functional group bromine atom with chain transfer reactivity is connected to the terminal carbon atom of the fatty acid chain segment.
On one hand, the bromine atom with reactivity is connected to the terminal carbon atom of the fatty acid chain segment, compared with other chain transfer agents, the molecular structure has higher functionality and branching degree, meanwhile, the molecular structure does not influence the reactivity of bromine, and the structure is stable in the reaction process and can keep lasting reactivity; on the other hand, the methacrylate chain segment can be copolymerized with a polymer matrix, so that no small molecules are remained in a reaction system in the chain transfer reaction process, the small molecules remained in the reaction system can influence the chain transfer reaction, and meanwhile, an additional impurity removal step is required, so that the method is complicated.
The synergistic effect between these two structures enables the branched compounds of the invention to retain a long-lasting reactivity during the reaction.
Preferably, n is 0.
Preferably, X 1 、X 2 、X 3 All are Br. The bromine is all attached to the same carbon atom, giving the compound a higher functionality and branching.
According to the preparation method of the compound capable of being branched, methacrylate glycidyl ether, bromine-containing aliphatic carboxylic acid shown as a formula II and a catalyst are subjected to ring opening reaction at 40-100 ℃ to obtain the compound capable of being branched;
in the formula II and the formula I, the same substituent groups have the same meanings.
The reaction of the preparation method is that the epoxy group in the glycidyl ether of the methacrylate and the carboxylic acid group in the bromine-containing aliphatic carboxylic acid are subjected to ring-opening reaction.
Preferably, the bromine-containing aliphatic carboxylic acid is any one of tribromoacetic acid, tribromopropionic acid, tribromobutyric acid, dibromoacetic acid, dibromopropionic acid, dibromobutyric acid, bromoacetic acid, bromopropionic acid or bromobutyric acid.
Preferably, the molar ratio of the methacrylate glycidyl ether to the bromine-containing aliphatic carboxylic acid is 1 to 1.2.
Preferably, the catalyst is one or a combination of several of tertiary amine, pyridine derivatives, quaternary ammonium salt, chromium acetylacetonate, lewis acid and triphenylphosphine.
Preferably, the temperature of the ring-opening reaction is 80 to 120 ℃.
Preferably, the end point of the ring-opening reaction is the acid value in the system <3mgKOH/g.
In order to ensure the stability of the methacrylate ester bond during the reaction of the branched monomer, a polymerization inhibitor may be added. The polymerization inhibitor is one or a combination of several of p-hydroxyanisole, dibutyl hydroxy toluene or phenothiazine.
The use of the above-mentioned compounds which can be branched for the preparation of branched cycloaliphatic resins is also within the scope of the present invention.
The invention also provides a preparation method of the branched alicyclic resin, which comprises the following steps:
s1, alicyclic epoxy resin, methacrylate, a thermal initiator, the branched compound (CTA-Br) and a catalyst react for 8-24 hours at the temperature of 40-120 ℃ to obtain branched alicyclic epoxy resin;
s2, reacting the product branched alicyclic epoxy resin obtained in the step S1, acrylic acid, dianhydride, a catalyst and a polymerization inhibitor at the temperature of 40-120 ℃ for 6-24 hours to obtain the branched alicyclic resin.
According to the preparation method of the branched alicyclic resin, the compound capable of being branched is selected as the chain transfer agent, the compound has high chain transfer activity, namely branching activity, and the prepared branched alicyclic resin is higher in branching degree and further lower in viscosity; meanwhile, the high branching degree is also beneficial to grafting more acrylate groups and carboxyl groups, so that the material has higher acid resistance; and the branched alicyclic resin has a large number of alicyclic structures, so that the dielectric constant of the material is favorably reduced, and the prepared material can be used for preparing a 5G material.
Preferably, the alicyclic epoxy resin is one or a combination of more of 1, 2-epoxy-4-vinylcyclohexane, 1, 2-epoxy-3-vinylcyclohexane, 1-epoxy ethyl-4-vinylcyclohexane or 1-epoxy ethyl-2-vinylcyclohexane.
Preferably, the methacrylate is one or a combination of Methyl Methacrylate (MMA), ethyl Methacrylate (EMA), n-butyl methacrylate (n-BMA), isobornyl methacrylate (IBMOA), lauryl Methacrylate (LMA) or hydroxyethyl methacrylate (HEMA).
Preferably, the thermal initiator in step S1 is one or a combination of two of azo type initiator or peroxide initiator.
Further preferably, the thermal initiator is one or a combination of Azodiisobutyronitrile (AIBN), benzoyl Peroxide (BPO) or potassium persulfate.
Preferably, the molar ratio of the alicyclic epoxy resin to the methacrylate in step S1 is 60 to 80.
Preferably, the ratio of the total number of moles of the cycloaliphatic epoxy resin and the methacrylate ester to the number of moles of the CTA-Br in step S1 is 1.
Preferably, the ratio of the total number of moles of the cycloaliphatic epoxy resin and the methacrylate to the number of moles of the thermal initiator in step S1 is 1.
Preferably, the dianhydride in step S2 is one or a combination of two or more of dianhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride or maleic anhydride.
Preferably, the catalyst in step S2 is one or a combination of several of tertiary amine, pyridine derivative, quaternary ammonium salt, chromium acetylacetonate, lewis acid or triphenylphosphine.
Preferably, in step S2, the molar ratio of epoxy group to acrylic acid to dianhydride in the product obtained in S1 is 2 to 3.
Compared with the prior art, the invention has the following beneficial effects:
the branched compound of the invention contains both a methacrylate structure and a functional group bromine with chain transfer reaction activity, the structure can be stably stored, the carried acrylate group can be bonded in copolymerization reaction, and no small molecule is remained in a resin system after the reaction is finished. The branched alicyclic epoxy acrylate resin has a plurality of acrylate groups, so that the branched alicyclic epoxy acrylate resin has good crosslinking density to prevent solution penetration, and has carboxylic acid groups, so that the resin has good acid resistance, and a large number of branched alicyclic structures cause the resin to have a relatively low dielectric constant; therefore, the solder mask has good chemical tin plating resistance (the chemical tin plating resistance is acid resistance and permeability resistance) when being applied to the protection of coatings in circuit boards, and is expected to be applied to PCB solder mask ink in 5G communication materials.
Drawings
FIG. 1 shows the intrinsic viscosity of branched alicyclic epoxy resins B-01 and B-02 prepared in examples 3 to 5 and linear alicyclic epoxy resin B-01A prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
This example provides a compound (CTA-Br) having a branching structure such as that shown below:
the preparation method comprises the following steps:
glycidyl methacrylate (149.26g, 1.05mol), triphenylphosphine (0.15g, 1000ppm) as a catalyst and p-hydroxyanisole (0.07g, 500ppm) as a polymerization inhibitor are added into a 500mL flask, the mixture is stirred uniformly, tribromoacetic acid (296.75g, 1mol) is added dropwise, after the dropwise addition is completed, the reaction is carried out at 80 ℃, and when the acid value in a reaction system is less than 3mgKOH/g, the reaction is stopped, and a clear, transparent and colorless compound (CTA-Br) with a branched structure is obtained.
The nuclear magnetic resonance data of the resulting branched structure compound (CTA-Br) were: 1 H NMR(400MHz,CDCl 3 ，ppm)6.52(s，1H)，6.40(s，1H)，5.67(s，1H)4.89(t，1H)，4.10-4.42(m，4H)，2.08(s，3H)。
example 2
This example provides a compound of branched structure (CTA-Br), such as shown below:
in the formula, n =1.
The preparation method differs from the example 1 in that: tribromoacetic acid was replaced with 3-bromopropionic acid (152.97g, 1mol). The nuclear magnetic resonance data of the resulting compound with a branched structure (CTA-Br) were: 1 H NMR(400MHz,CDCl 3 ，ppm)6.48(s，1H)，6.38(s，1H)，5.70(s，1H)4.59(t，1H)，4.10-4.39(m，4H)，3.58(t，2H)，2.65(m,2H)2.02(s，3H)。
example 3
This example provides a branched cycloaliphatic resin, the preparation method comprising the steps of:
s1, adding 160g of 1, 2-epoxy-4-vinyl cyclohexane and 30g of ethyl methacrylate into a 500mL flask, adding 8g of CTA-Br prepared in example 1 as a chain transfer agent, 2g of Azobisisobutyronitrile (AIBN) as an initiator, adding 100g of ethyl acetate as a solvent, introducing nitrogen for 30min, and reacting at 60 ℃ for 12h to obtain branched alicyclic epoxy resin B-01;
the polymer was analyzed by a common volume exclusion chromatograph and a triple detection gel permeation chromatograph, with the following results: the weight average molecular weight Mw is measured by a common volume exclusion chromatograph, SEC =129000g/mol, the light scattering weight average molecular weight Mw is measured by a triple detection gel permeation chromatograph, and MALLS =131000g/mol;
the epoxy equivalent of B-01 is measured to be 0.56mol/100g of sample by the method of GB/T4612-2008 'determination of epoxy equivalent of plastic epoxy compound';
s2, adding 1 into a 250mL flaskHeating branched alicyclic epoxy resin B-01 prepared from 00g S1, 20g of acrylic acid, 12g of succinic anhydride, 0.13g of catalyst triphenylphosphine and 0.13g of polymerization inhibitor p-hydroxyphenyl ether to 110 ℃, reacting until the acid value is less than 3mgKOH/g of sample, cooling, discharging to obtain branched alicyclic acrylate resin M containing carboxyl 1 . Viscosity at 60 ℃ of 11230cps, and dielectric constant Dk =3.18 measured by impedance analyzer (Agilent technologies, ltd.).
Example 4
This example provides a branched cycloaliphatic resin, prepared differently from example 3 in that: 12g of succinic anhydride was replaced by 25.53g of tetrahydrophthalic anhydride in step S2. Obtaining a branched alicyclic acrylate resin M containing carboxyl 2 . Viscosity at 60 ℃ was 15800cps, and dielectric constant Dk =3.21 was measured by impedance analyzer (Agilent technologies, ltd.).
Example 5
This example provides a branched cycloaliphatic resin, which differs from example 3 in the method of preparation: the chain transfer agent in S1 was replaced with CTA-Br obtained in example 2 to obtain a branched alicyclic epoxy resin B-02. Obtaining the branched alicyclic acrylate resin M containing carboxyl 3 . The viscosity at 60 ℃ was 12300cps, and the dielectric constant Dk =3.19 was measured by an impedance analyzer (Agilent technologies, ltd.).
Comparative example 1
This comparative example provides a linear cycloaliphatic epoxy resin B-01A, which is prepared by a method different from that of example 3 in that:
CTA-Br prepared in example 1 was not added in step S1 as a chain transfer agent;
in the step S2, the branched alicyclic epoxy resin B-01 is replaced by the linear alicyclic epoxy resin B-01A to prepare the linear alicyclic epoxy acrylate resin M with carboxyl 0 . Obtaining the linear alicyclic epoxy acrylate resin M containing carboxyl 0 And a viscosity of 26500cps at 60 ℃ and a dielectric constant Dk =3.48 measured by an impedance analyzer (Agilent technologies, ltd.).
Branched esters prepared from examples 3/4/5Ring family epoxy acrylate resin M 1 、M 2 、M 3 The viscosity and dielectric constant Dk of (1) are compared with those of the linear alicyclic epoxy acrylate resin M prepared by the comparative example 1 0 Indicating that the branched structure can reduce the viscosity and dielectric constant of the resin.
Performance analysis
1. Comparative analyses were made on the branching degrees of the branched alicyclic epoxy resins B-01 and B-02 prepared in examples 3 to 5 and the linear alicyclic epoxy resin B-01A prepared in comparative example 1.
The branching degree analysis adopts a characteristic constant alpha in a Mark-Houwink equation [ eta ] = K [ M ] alpha to judge the polymerization degree of the branched polymer, the lower the alpha value is, the higher the branching degree of the polymer is, namely lg [ eta ] = alpha lg [ M ] + alpha lgK (alpha and K are constants, eta is an intrinsic viscosity, M is a number average molecular weight), namely the lower the slope is in a linear function of lg [ eta ] to lg [ M ], the lower the alpha value is, and the higher the branching degree of the polymer is.
The results of intrinsic viscosity versus the corresponding molecular weight are shown in FIG. 1, and the intrinsic viscosity of the branched alicyclic epoxy resin B-01 prepared in example 3 and the branched alicyclic epoxy resin B-02 prepared in example 5 is smaller than the linear characteristic constant α of the corresponding molecular weight, demonstrating the presence of a branched structure.
2. Branched alicyclic acrylate resins M containing carboxyl groups prepared in examples and comparative examples 0 、M 1 、M 2 And M 3 The acid resistance of (2) was tested: 80g of carboxyl-containing branched alicyclic acrylate resin, 20g1, 6-hexanediol diacrylate HDDA and 3g of photoinitiator 1173 are uniformly stirred to obtain a mixture, a 12-micrometer wire bar is selected to scrape the mixture on a PC board, a medium-pressure mercury lamp is used for carrying out radiation curing for 10s, and the light intensity is 200mJ cm -2 And completely curing the coating to obtain the coated plate. Two plates were prepared for each sample. The acid resistance of the resin is measured by a soaking method: the cured coated plate was completely immersed in a 0.05mol/L sulfuric acid solution at 20 ℃ for 30 minutes.
1) And observing whether the coating has the phenomena of light loss, color change, bubbling, spots, falling off and the like. If none, the coating is intact, indicated as "OK"; any change in loss of gloss, discoloration, blistering, spotting, flaking, etc., indicates that the coating is damaged, as indicated by "NG". "OK" indicates that the coating has good acid resistance, i.e. the resin has good acid resistance.
2) Meanwhile, a WGG60-E4 single-angle 60-degree gloss instrument (Quanzhou Keshi good photoelectric instrument research institute) is adopted to measure the gloss change of the coating before and after soaking, and the gloss test is carried out according to ASTM-D523; the adhesion test before and after the coating is soaked adopts a hundred-grid test method, the GB/T9286 and ISO 2409 standards are adopted for measurement, and the test result is represented by 'A/B', wherein A represents the glossiness of the coating before soaking or intact grids in the hundred-grid test, and B represents the glossiness of the coating after soaking or intact grids in the hundred-grid test.
The test results are detailed in table 1.
TABLE 1 results of performance test of resins obtained in examples 3 to 5 and comparative example
As is clear from the results in Table 1, the resins M obtained in examples 3 to 5 1 、M 2 And M 3 The surface of the prepared photocureable coating is intact after being soaked in sulfuric acid solution at the temperature of 20 ℃; and the glossiness and the adhesive force performance are not changed before and after soaking, the resin M is synthesized 1 、M 2 And M 3 Has good acid resistance and good acid resistance; whereas the linear alicyclic epoxy resin B-01A of comparative example 1 was inferior in acid resistance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. Use of a branchable compound as a chain transfer agent in the preparation of a branched cycloaliphatic resin, characterised in that the branchable compound has the structure shown in formula (I):
wherein n is an integer between 0 and 3; x 1 、X 2 、X 3 Independently selected from Br or H, and X 1 、X 2 And X 3 At least one of which is Br.
2. The use according to claim 1, wherein n is 0.
3. Use according to claim 1, characterized in that X 1 、X 2 、X 3 Are all Br.
4. Use according to claim 1, wherein the compound capable of branching is prepared by: carrying out ring-opening reaction on methacrylate glycidyl ether, bromine-containing aliphatic carboxylic acid shown as a formula II and a catalyst at 40-100 ℃ to obtain a compound with a branched structure;
5. the use according to claim 4, wherein the molar ratio of methacrylate glycidyl ether to bromine-containing aliphatic carboxylic acid is 1 to 1.2.
6. A method of preparing a branched cycloaliphatic resin, comprising the steps of:
s1, alicyclic epoxy resin, methacrylate, an initiator, the compound capable of being branched in the claims 1-3 and a catalyst react for 8-24 hours at the temperature of 40-120 ℃ to obtain branched alicyclic epoxy resin;
s2, reacting the branched alicyclic epoxy resin obtained in the step S1, acrylic acid, dianhydride, a catalyst and a polymerization inhibitor at the temperature of 40-120 ℃ for 6-24 hours to obtain the branched alicyclic resin.
7. The method for preparing the branched alicyclic resin according to claim 6, wherein the alicyclic epoxy resin is one or a combination of 1, 2-epoxy-4-vinylcyclohexane, 1, 2-epoxy-3-vinylcyclohexane, 1-epoxyethyl-4-vinylcyclohexane or 1-epoxyethyl-2-vinylcyclohexane.
8. The method for preparing the branched alicyclic resin according to claim 6, wherein the methacrylate is one or a combination of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, lauryl methacrylate or hydroxyethyl methacrylate.
9. The method of claim 6, wherein the ratio of the total number of moles of the cycloaliphatic epoxy resin and the methacrylate to the number of moles of the compound capable of branching is 1.
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