CN111484592B - Isocyanate-polybutadiene-epoxy resin segmented copolymer, preparation method and application thereof, and prepared resin composition and copper-clad plate - Google Patents
Isocyanate-polybutadiene-epoxy resin segmented copolymer, preparation method and application thereof, and prepared resin composition and copper-clad plate Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention discloses an isocyanate-polybutadiene-epoxy resin segmented copolymer, a preparation method and application thereof, and a prepared resin composition and a copper-clad plate. The preparation method comprises the following steps: and (2) reacting the isocyanate-terminated hydroxyl-terminated polybutadiene, bisphenol A glycidyl ether type epoxy resin and multifunctional epoxy resin under the action of a catalyst dibutyltin dilaurate to obtain the isocyanate-polybutadiene-epoxy resin segmented copolymer. The novel low-dielectric-constant copper-clad plate is prepared by dipping the quartz glass fiber cloth in the isocyanate-polybutadiene-epoxy resin segmented copolymer modified epoxy resin, has the characteristics of easily available raw materials, low cost and convenient processing, has excellent dielectric property, high glass transition temperature, good mechanical strength and flame retardant property, and provides a new idea for preparing the low-dielectric-constant copper-clad plate.
Description
Technical Field
The invention relates to an isocyanate-polybutadiene-epoxy resin segmented copolymer, a preparation method and application thereof, and a prepared resin composition and a copper-clad plate.
Background
The dielectric constant (Dk) refers to the ratio of the capacitance of the same capacitor in a dielectric medium to its capacitance in vacuum, and generally represents the magnitude of the charge storage capacity of a material. The higher the dielectric polarizability, the greater its ability to store charge, the higher the dielectric constant, and thus its ability to block signal transmission. The dielectric constant determines the speed at which an electrical signal propagates through the medium. The lower the dielectric constant, the faster the signal transmission speed. With the development of electronic technology, advanced communication equipment and technology, the demand of various high-end electronic equipment widely applied to the communication field is rapidly increasing, in order to meet the requirements of high transmission speed and low loss of signal transmission of electronic equipment, the research on low dielectric constant materials in the semiconductor industry is also increasing, and copper-clad plate base materials with various dielectric constants (Dk) and dielectric loss (Df) are also continuously developing.
The copper-clad plate is composed of resin, a reinforcing material and a conductive copper foil, a capacitor structure is formed, and the dielectric constant of the dielectric medium of the resin and the reinforcing material has direct influence on the signal transmission speed.
The existing low-dielectric-constant copper-clad plate is generally made of resins such as polytetrafluoroethylene resin, cyanate ester, polyphenyl ether, polyimide resin, hydrocarbon resin, epoxy resin with a biphenyl structure or a dicyclopentadiene structure or a naphthalene ring structure, maleimide triazine modified phenolic resin or alkyl modified phenolic resin, styrene maleic anhydride copolymer, BT and the like, and has the common characteristic that a molecular structure contains nonpolar or weakly polar groups, so that the polarizability of the material in an electric field can be reduced. The copper-clad plate made of the materials has good dielectric property, but has the defects of complex process, high cost and difficult processing.
Disclosure of Invention
The invention aims to solve the technical problems that the raw material cost for preparing a copper-clad plate is high, the processing is inconvenient, and the prepared copper-clad plate cannot give consideration to the defects of dielectric property, glass transition temperature, mechanical strength, flame retardant property and the like, and provides an isocyanate-polybutadiene-epoxy resin segmented copolymer, a preparation method and application thereof, and a prepared resin composition and a copper-clad plate, especially a low-dielectric-constant copper-clad plate. The novel copper-clad plate with low dielectric constant is prepared by using the isocyanate-polybutadiene-epoxy resin segmented copolymer or the resin composition prepared by using the same, and has excellent dielectric property, high glass transition temperature, good mechanical strength and flame retardant property.
The invention provides a preparation method of an isocyanate-polybutadiene-epoxy resin block copolymer, which comprises the following steps:
and (2) reacting isocyanate-terminated hydroxyl-terminated polybutadiene (ITPB), bisphenol A glycidyl ether type epoxy resin (DGEBA) and a mixture of multifunctional epoxy resin under the action of a catalyst dibutyltin dilaurate (DBTDL) to obtain the isocyanate-polybutadiene-epoxy resin segmented copolymer.
The reaction temperature may be conventional in the art, preferably 78-82 deg.C, more preferably 80 deg.C.
The reaction time may be conventional in the art, and is preferably 105 to 135 minutes, and more preferably 120 minutes.
The molar ratio of the isocyanate terminated hydroxyl terminated polybutadiene to the multifunctional epoxy resin may be conventional in the art, and is preferably 1:0.225 to 0.275, more preferably 1: 0.25.
The molar ratio of the isocyanate-terminated hydroxyl-terminated polybutadiene to the bisphenol a glycidyl ether type epoxy resin can be conventional in the art, and is preferably 1: 0.675-0.825, and more preferably 1: 0.75.
After the inventor tries, if the relative dosage of the isocyanate-terminated hydroxyl-terminated polybutadiene is high, when the prepared isocyanate-polybutadiene-epoxy resin segmented copolymer is used for preparing a copper-clad plate, the glass transition temperature of a finally prepared product is low; if the relative amount of the epoxy resin is too high, the prepared isocyanate-polybutadiene-epoxy resin segmented copolymer has high dielectric constant when being used for preparing a copper-clad plate.
The amount of dibutyltin dilaurate used as the catalyst can be conventional in the art, and is preferably 0.15-0.3%, preferably 0.25% by mass of the isocyanate-terminated hydroxyl-terminated polybutadiene.
The bisphenol a glycidyl ether type epoxy resin can be conventional in the art, and the average molecular weight thereof is preferably 360 to 400, more preferably 388; the epoxy equivalent is preferably 180 to 200g/eq, more preferably 194 g/eq; the bisphenol A glycidyl ether type epoxy resin is preferably purchased from BE188 of chemical engineering of Changchun.
The multifunctional epoxy resin may be a multifunctional epoxy resin conventionally used in the art, preferably selected from one or more of resorcinol formaldehyde epoxy resin, tetraglycidyl ether tetraphenylethane, triglycidyl ether triphenylmethane, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol and glycidyl m-xylylenediamine, preferably novolac epoxy resin, more preferably o-cresol novolac epoxy resin. The o-cresol novolac epoxy resin is preferably purchased from CNE200 of chemical industry of Changchun.
The average molecular weight of the multifunctional epoxy resin is preferably 400 to 600, more preferably 500; the epoxy equivalent is preferably 180 to 220g/eq, more preferably 200 g/eq.
The isocyanate-terminated hydroxyl-terminated polybutadiene may be an isocyanate-terminated hydroxyl-terminated polybutadiene as is conventional in the art, such as F bi l.
Soares B G.Modification of epoxy resin by isocyanate-terminated polybutadiene[J]Journal of Applied Polymer Science,2002,83(4): 838-. Preferably, the preparation method comprises the following steps: heating a mixture of hydroxyl-terminated polybutadiene and a catalyst dibutyltin dilaurate, carrying out vacuum dehydration, mixing with the toluene diisocyanate, and carrying out esterification reaction to obtain the catalyst.
The temperature after mixing and heating can be conventional in the art, preferably 85-95 ℃, and more preferably 90 ℃;
in order to ensure complete dehydration, the vacuum dehydration time is preferably 20 to 40 minutes, and more preferably 30 minutes.
The esterification reaction time can be conventional in the art, and is preferably 130 to 170 minutes, and more preferably 150 minutes.
The temperature of the esterification reaction can be conventional in the art, and is preferably 78 to 82 ℃, more preferably 80 ℃.
The esterification reaction is preferably carried out in the presence of an inert atmosphere, preferably nitrogen.
The molar ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is preferably 1: 1-1.1.
The amount of the dibutyltin dilaurate serving as the catalyst can be conventional in the field, and preferably accounts for 0.35-0.6%, and preferably 0.5% of the mass of the hydroxyl-terminated polybutadiene.
The hydroxyl value of the hydroxyl-terminated polybutadiene is preferably 0.6 to 0.7mmol/g, more preferably 0.66 mmol/g; the number average molecular weight is preferably 2500 to 3500, more preferably 2980.
The toluene diisocyanate preferably consists of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and the mass percentage of the 2, 4-toluene diisocyanate to the 2, 6-toluene diisocyanate is 80: 20.
The preparation method as described above, preferably comprising the steps of:
(1) heating the mixture of the hydroxyl-terminated polybutadiene and the catalyst dibutyltin dilaurate, carrying out vacuum dehydration, mixing with the toluene diisocyanate, and carrying out the esterification reaction;
(2) and adding the bisphenol A glycidyl ether type epoxy resin and the multifunctional epoxy resin, and reacting to obtain the isocyanate-polybutadiene-epoxy resin segmented copolymer.
The above preparation method preferably further comprises adding propylene glycol methyl ether and acetone after the reaction to dissolve the isocyanate-polybutadiene-epoxy resin block copolymer into a liquid for subsequent use, and may be replaced by acetone, ethylene glycol methyl ether, etc., the added amount of the propylene glycol methyl ether and the acetone being determined according to the amount of the isocyanate-polybutadiene-epoxy resin block copolymer, which may be conventional in the art.
The invention also provides an isocyanate-polybutadiene-epoxy resin block copolymer prepared according to the preparation method.
The invention also provides an application of the isocyanate-polybutadiene-epoxy resin block copolymer in an epoxy resin composition or a copper-clad plate.
The invention also provides an epoxy resin composition, which comprises the following components in parts by weight:
70-95 parts of brominated epoxy resin, 5-30 parts of the isocyanate-polybutadiene-epoxy resin segmented copolymer, 2.5-2.7 parts of dicyandiamide, 0.08-0.1 part of 2-ethyl-4-methylimidazole, 10-30 parts of silicon micropowder and 25-50 parts of dimethylformamide, wherein:
the amount of the brominated epoxy resin is preferably 75-90 parts, and more preferably 80-85 parts.
The isocyanate-polybutadiene-epoxy resin block copolymer is preferably used in an amount of 10 to 25 parts, more preferably 15 to 20 parts.
The amount of dicyandiamide used is preferably 2.6 parts.
The amount of the 2-ethyl-4-methylimidazole used is preferably 0.09 part.
The amount of the dimethylformamide is preferably 30 parts.
The equivalent weight of the brominated epoxy resin is preferably 280-460 g/eq, and more preferably 435 g/eq.
The bromine content of the brominated epoxy resin is preferably 19-21%, and the percentage is weight percentage.
The average particle diameter D50 of the silica micropowder is preferably 1-2 μm, and the silica micropowder whose surface is treated with KH-550 or KH-560 silane coupling agent is more preferred.
The present invention also provides a method for preparing the epoxy resin composition, which comprises the following steps:
carrying out high shearing, mixing and emulsifying on the mixture of the brominated epoxy resin, the isocyanate-polybutadiene-epoxy resin segmented copolymer, the dicyandiamide, the 2-ethyl-4-methylimidazole, the silicon micropowder and the dimethylformamide, and curing to obtain the modified polyurethane; wherein:
the emulsifying time is preferably 5 to 10 minutes.
The curing time is preferably 8 to 16 hours.
The invention also provides a copper-clad plate prepared by using the epoxy resin composition.
The preparation of the copper-clad plate can be conventional in the field, and comprises the following steps: the low-dielectric-constant quartz glass fiber cloth is used as a reinforcing material, is pretreated by a silane coupling agent containing epoxy groups, is then impregnated with the epoxy resin composition, and is baked and pressed to obtain a finished product.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the novel low-dielectric-constant copper-clad plate is prepared by dipping the quartz glass fiber cloth in the isocyanate-polybutadiene-epoxy resin segmented copolymer modified epoxy resin, has the characteristics of easily available raw materials, low cost and convenient processing, has excellent dielectric property, high glass transition temperature, good mechanical strength and flame retardant property, and provides a new idea for preparing the low-dielectric-constant copper-clad plate.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The bisphenol A glycidyl ether type epoxy resin used in the following examples was purchased from Catharanthus roseus chemical BE188, and the o-cresol novolac epoxy resin was purchased from Catharanthus roseus chemical CNE 200.
EXAMPLE 1 preparation of epoxy resin-isocyanate-polybutadiene Block copolymer
150g of hydroxyl-terminated polybutadiene (HTPB) (hydroxyl value 0.66mmol/g, number average molecular weight Mn 2980) and 0.75g of dibutyltin dilaurate (DBTDL) catalyst are added into a 500ml three-neck flask provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel, stirred and heated to 90 +/-5 ℃, vacuum dehydrated for 30 minutes, cooled to 40 +/-2 ℃, filled with nitrogen gas in the flask, added with 36.5g of toluene diisocyanate (the mass percentage of 2,4-TDI to 2,6-TDI is 80:20), slowly heated to 80 +/-2 ℃ and reacted for 2.5 hours. Then, 29g of bisphenol A glycidyl ether type epoxy resin (molecular weight: 388, epoxy equivalent: 194g/eq) and 11.9g of o-cresol novolac epoxy resin (molecular weight: 500, epoxy equivalent: 200g/eq) were added and the reaction was continued at 80. + -. 2 ℃ for 2 hours. After the reaction, 50g of propylene glycol methyl ether and 26g of butanone are added, and the epoxy resin-isocyanate-polybutadiene segmented copolymer (EITPB) is prepared after discharging.
The molar ratio of each reaction component is as follows:
HTPB is toluene diisocyanate, bisphenol A glycidyl ether type epoxy resin and o-cresol novolac epoxy resin which are 1:1:0.75: 0.25.
The dosage of dibutyltin dilaurate DBTDL is 0.5 percent of the mass of HTPB.
Embodiment 2 production of copper-clad plate with low dielectric constant
The brominated epoxy resin has an epoxy equivalent of 435g/eq and a bromine content of 19-21%; the silicon micropowder D50: 1 to 2 μm, and treating the surface with KH-550 or KH-560 silane coupling agent
After the materials are mixed according to the mass ratio, the materials are subjected to high-shear mixing emulsification for 5-10 minutes and then cured for 8-16 hours, and the epoxy resin composition is prepared.
Quartz glass fiber cloth (100-110 g/m)2) Impregnating the epoxy resin composition, baking at 170 ℃ for 3-4 minutes to obtain a bonding sheet, and controlling the unit weight of the bonding sheet to be 200-250 g/m2. Laminating 5 bonding sheets together, coating a layer of copper foil with a thickness of 18 μm on each of two surfaces, placing the two sheets between two stainless steel plates with smooth surfaces, placing the two sheets in a vacuum press, and controlling the unit pressure at 30-40 kgf/cm2And controlling the temperature at 170-190 ℃, keeping the temperature for 60 minutes, and cooling to obtain the copper-clad plate with the thickness of 0.5 mm.
Other examples and comparative examples were all made into copper clad laminates according to the above method, and the formula and performance test results are shown in table 1.
TABLE 1
According to the table 1, the final copper-clad plate prepared has the advantages that under the condition that other parameters are basically equivalent to those of the prior art, the dielectric constant and the dielectric loss tangent are obviously reduced, and the thermal stress and the glass transition temperature are obviously improved.
Claims (15)
1. A method for preparing an isocyanate-polybutadiene-epoxy block copolymer, comprising the steps of:
reacting isocyanate-terminated hydroxyl-terminated polybutadiene, bisphenol A glycidyl ether type epoxy resin and multifunctional epoxy resin under the action of a catalyst dibutyltin dilaurate to obtain the isocyanate-polybutadiene-epoxy resin segmented copolymer;
the multifunctional epoxy resin is o-cresol novolac epoxy resin;
the molar ratio of the isocyanate-terminated hydroxyl-terminated polybutadiene to the multifunctional epoxy resin is 1: 0.225-0.275; the molar ratio of the isocyanate-terminated hydroxyl-terminated polybutadiene to the bisphenol A glycidyl ether type epoxy resin is 1: 0.675-0.825;
the bisphenol A glycidyl ether type epoxy resin has an average molecular weight of 360-400 and an epoxy equivalent of 180-200 g/eq;
the average molecular weight of the multifunctional epoxy resin is 400-600; the epoxy equivalent is 180 to 220 g/eq.
2. The preparation method according to claim 1, wherein the reaction temperature is 78-82 ℃;
and/or the reaction time is 105-135 minutes;
and/or the molar ratio of the isocyanate-terminated hydroxyl-terminated polybutadiene to the multifunctional epoxy resin is 1: 0.25; the molar ratio of the isocyanate-terminated hydroxyl-terminated polybutadiene to the bisphenol A glycidyl ether type epoxy resin is 1: 0.75;
and/or the dosage of the catalyst dibutyltin dilaurate accounts for 0.15-0.3% of the isocyanate-terminated hydroxyl-terminated polybutadiene, and the percentage is mass percent.
3. The method of claim 2, wherein the reaction temperature is 80 ℃;
and/or the reaction time is 120 minutes;
and/or the amount of the catalyst dibutyltin dilaurate accounts for 0.25% of the isocyanate-terminated hydroxyl-terminated polybutadiene, and the percentage is mass percentage;
and/or the bisphenol a glycidyl ether type epoxy resin has an average molecular weight of 388; the epoxy equivalent is 194 g/eq;
the multifunctional epoxy resin has an average molecular weight of 500; the epoxy equivalent was 200 g/eq.
4. The process according to any one of claims 1 to 3, wherein the isocyanate-terminated hydroxyl-terminated polybutadiene is obtained by the following process:
heating a mixture of hydroxyl-terminated polybutadiene and a catalyst dibutyltin dilaurate, carrying out vacuum dehydration, mixing with toluene diisocyanate, and reacting to obtain the catalyst.
5. The method according to claim 4, wherein the temperature of the mixture after heating is 85 to 95 ℃;
and/or the vacuum dehydration time is 20-40 minutes;
and/or the reaction time is 130-170 minutes;
and/or the reaction temperature is 78-82 ℃;
and/or, the reaction is carried out in the presence of an inert atmosphere;
and/or the molar ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is 1: 1-1.1;
and/or the dosage of the dibutyltin dilaurate catalyst accounts for 0.35-0.6% of the mass of the hydroxyl-terminated polybutadiene;
and/or the hydroxyl value of the hydroxyl-terminated polybutadiene is 0.6-0.7 mmol/g; the number average molecular weight is 2500-3500;
and/or the toluene diisocyanate consists of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and the mass percentage of the 2, 4-toluene diisocyanate to the 2, 6-toluene diisocyanate is 80: 20.
6. The method of claim 5, wherein the temperature of the mixture after heating is 90 ℃;
and/or the vacuum dehydration time is 30 minutes;
and/or the reaction time is 150 minutes;
and/or the temperature of the reaction is 80 ℃;
and/or the inert atmosphere is nitrogen;
and/or the amount of the dibutyltin dilaurate serving as the catalyst accounts for 0.5% of the mass of the hydroxyl-terminated polybutadiene;
and/or the hydroxyl value of the hydroxyl-terminated polybutadiene is 0.66 mmol/g; the number average molecular weight was 2980.
7. The method according to any one of claims 1 to 3 and 5 to 6, wherein the method comprises the steps of:
(1) heating the mixture of the hydroxyl-terminated polybutadiene and the catalyst dibutyltin dilaurate, carrying out vacuum dehydration, mixing with toluene diisocyanate, and carrying out reaction;
(2) adding the bisphenol A glycidyl ether type epoxy resin and the functional epoxy resin, and reacting to obtain the isocyanate-polybutadiene-epoxy resin segmented copolymer.
8. An isocyanate-polybutadiene-epoxy resin block copolymer prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the isocyanate-polybutadiene-epoxy block copolymer according to claim 8 in epoxy resin compositions or copper clad laminates.
10. The epoxy resin composition is characterized by comprising the following components in parts by weight:
70 to 95 parts of brominated epoxy resin, 5 to 30 parts of isocyanate-polybutadiene-epoxy resin block copolymer according to claim 8, 2.5 to 2.7 parts of dicyandiamide, 0.08 to 0.1 part of 2-ethyl-4-methylimidazole, 10 to 30 parts of fine silica powder and 25 to 50 parts of dimethylformamide.
11. The epoxy resin composition according to claim 10,
the using amount of the brominated epoxy resin is 75-90 parts;
and/or the isocyanate-polybutadiene-epoxy resin block copolymer is used in an amount of 10-25 parts;
and/or the amount of dicyandiamide used is 2.6 parts;
and/or the dosage of the 2-ethyl-4-methylimidazole is 0.09 part;
and/or the amount of the dimethylformamide is 30 parts;
and/or the equivalent weight of the brominated epoxy resin is 280-460 g/eq; the bromine content is 19-21%, and the percentage is weight percentage;
and/or the average particle size D50 of the silicon micropowder is 1-2 μm.
12. The epoxy resin composition according to claim 11,
the using amount of the brominated epoxy resin is 80-85 parts;
and/or the usage amount of the isocyanate-polybutadiene-epoxy resin block copolymer is 15-20 parts;
and/or the equivalent weight of the brominated epoxy resin is 435 g/eq;
and/or the silica micropowder is treated by using a KH-550 or KH-560 silane coupling agent on the surface of the silica micropowder.
13. A method for preparing the epoxy resin composition according to any one of claims 11 to 12, comprising:
and (2) subjecting the mixture of the brominated epoxy resin, the isocyanate-polybutadiene-epoxy resin segmented copolymer, the dicyandiamide, the 2-ethyl-4-methylimidazole, the silica micropowder and the dimethylformamide to high shearing, mixing, emulsifying and curing to obtain the polyurethane adhesive.
14. The method of preparing the epoxy resin composition according to claim 13,
the emulsifying time is 5-10 minutes;
and/or the curing time is 8-16 hours.
15. A copper-clad plate prepared by using the epoxy resin composition as defined in any one of claims 10 to 12.
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| JPH1160677A (en) * | 1997-08-19 | 1999-03-02 | Hitachi Chem Co Ltd | Epoxy resin composition for printed wiring board, and prepreg and metal-clad laminate prepared by using the same |
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