CN111777541A - high-Tg low-dielectric active ester curing agent, preparation method and application - Google Patents
high-Tg low-dielectric active ester curing agent, preparation method and application Download PDFInfo
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- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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Abstract
The invention discloses a high Tg low dielectric active ester curing agent and a preparation method thereof, wherein the preparation method of the compound is as follows: reacting 3, 5-dicarboxylic acid aniline, maleic anhydride, acetic anhydride and a catalyst to obtain 5-maleimide-isophthalic acid; reacting 5-maleimide-m-phthalic acid with thionyl chloride to obtain 5-maleimide-isophthaloyl dichloride; adding aromatic phenol compound, acid-binding agent and solvent into a reactor, preparing a diacid chloride solution from 5-maleimide-isophthaloyl chloride, aromatic diacid chloride and solvent, and dropwise adding the solution into the reactorAfter the temperature rise reaction, monophenol compound is added for reaction, and then the curing agent with high Tg and low dielectric constant is prepared after filtration, washing, extraction, distillation and drying. The high Tg low-dielectric active ester curing agent can improve the heat resistance of an active ester cured epoxy resin-based laminated board, endows the laminated board with excellent dielectric property, and is suitable for the field of high-performance printed circuit boards.
Description
Technical Field
The invention belongs to an epoxy resin curing agent and preparation and application thereof, and relates to a high-Tg low-dielectric active ester curing agent, a preparation method and application thereof. The low-dielectric active ester curing agent with high Tg (Tg is the glass transition temperature for short) can be widely applied to the field of high-performance printed circuit boards.
Background
In recent years, with the increasing shortness, thinness, high performance and multifunctionality of electronic products, the number of electronic components is increased, the volume is reduced, the weight is lightened, and the integration level is continuously improved, so that higher requirements are put on substrate materials used for printed wiring boards bearing the electronic components, and the development trend that electronic signal processing and signal transmission are increasingly high-frequency and high-speed, and electronic components are highly accurately and highly integrated is met. The requirements for the substrate material include high heat resistance, excellent dielectric properties, low water absorption, good processability, and the like.
In a printed circuit board substrate, epoxy resin is widely applied due to good manufacturability and comprehensive performance, however, amines, linear phenolic resin, acid anhydride and the like are generally adopted as curing agents in a traditional epoxy resin-based laminated board, and a molecular chain contains a large amount of polar secondary hydroxyl groups, so that the dielectric performance of the laminated board is generally poor, for example, the dielectric constant of the FR-4 laminated board is 4.7-5.0 under 1MHz, and the dielectric loss is 0.015-0.019; the glass transition temperature of 145 ℃ (courage, Pipewai, etc.. polyphenyl ether/epoxy resin system [ J ] for high-performance copper-clad plates, plastic technology, 2006,34 (2)) cannot meet the performance requirements of low dielectric, high heat resistance, etc. required by the processing of current printed circuit boards and the design and use of electronic products. In the prior art, the application of active ester resin as an epoxy resin curing agent is widely concerned. The active ester resin as the curing agent can reduce secondary hydroxyl on a molecular chain of a cured epoxy resin and improve the dielectric property of the epoxy resin-based laminated board, however, an ester-based side chain with a plasticizing effect often damages the glass heat resistance of the laminated board, and the glass transition temperature of the epoxy resin-based laminated board is generally lower than that of the epoxy resin-based laminated board cured by polyamine or phenolic resin. CN 109265654A discloses a resin composition and a prepreg and a laminated board made of the same, which adopts epoxy resin, 1,1 ', 2, 2' -tetraphenylethane active ester curing agent and benzoxazine to form the resin composition, wherein the 1,1 ', 2, 2' -tetraphenylethane active ester curing agent can improve the crosslinking density of the cured epoxy resin and improve the heat resistance of the laminated board, but the glass transition temperature of the laminated board made of the epoxy resin and the 1,1 ', 2, 2' -tetraphenylethane active ester curing agent is lower than 190 ℃, and the heat resistance of the laminated board does not meet the application requirements of high-performance laminated boards such as high heat resistance, high frequency and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-Tg low-dielectric active ester curing agent, a preparation method and application. The high Tg low-dielectric active ester curing agent provided by the invention is polyester type active ester with maleimide groups, can generate double bond crosslinking reaction while curing epoxy resin, improves the crosslinking density of epoxy resin curing materials, achieves the purpose of improving the heat resistance of an active ester cured epoxy resin-based laminated board, and endows the laminated board with excellent dielectric property.
The content of the invention is as follows: a high Tg low dielectric active ester curing agent is characterized in that: the high Tg low dielectric active ester curing agent has a chemical structural general formula shown in (I):
in formula (I): m is 0-4, n is 0-4, and the sum of m and n is 0-8; r1Is composed of
Any one of (a); r2Is composed of
R3Is composed of
Any of the above.
The high Tg low dielectric active ester curing agent is yellow powder, the number average molecular weight is 931-2209, the molecular weight distribution index is 1.24-1.71, the softening point is 116-149 ℃, and the ester equivalent is 160-245 g/eq.
Another aspect of the invention is: a preparation method of a high Tg low dielectric active ester curing agent is characterized by comprising the following steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.11-0.15 mol of maleic anhydride in 75-130 ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the (dissolved) maleic anhydride solution into the reactor A at a dropping speed of 1-2 ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 2-3 h after dropwise adding is finished; then adding 0.14-0.2 mol of acetic anhydride and 0.0001-0.0008 mol of catalyst, heating to 60-65 ℃, reacting for 3-4 h, cooling, precipitating with (a large amount of) water (which can be tap water, deionized water or distilled water), filtering, washing, and recrystallizing to prepare 5-maleimide-isophthalic acid;
the catalyst is sodium acetate or nickel acetate;
the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 100-200 mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring and dissolving, dropwise adding 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dropwise adding is finished, slowly heating to 50-60 ℃, stirring for 2-3 h, distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl dichloride;
the solvent B is toluene or xylene;
c. adding 0.1mol of aromatic phenol compound, 0.3-0.65 mol of acid-binding agent and 100-200 mL of solvent C into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; adding 0.025-0.2 mol of 5-maleimide-isophthaloyl dichloride, 0-0.1 mol of aromatic diacid chloride and 200-500 mL of solvent C into a container E to prepare a diacid chloride solution, then dropwise adding the solution into a reactor D at a dropping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dropwise adding, stirring for 2-3 h, then adding 0.055-0.3 mol of monophenol compound, continuously stirring for 2-3 h, and carrying out filtering, alkali washing, water washing, extraction, distillation and drying (and the like) to obtain the high-Tg low-dielectric-activity ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane;
the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride;
the acid-binding agent is triethylamine or pyridine;
the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
In another aspect of the invention: in the step c, 0to 0.1mol of the aromatic diacid chloride can be replaced by 0.01 to 0.1mol of the aromatic diacid chloride.
Another aspect of the invention is: the application of the high Tg low dielectric active ester curing agent is characterized in that: the curing agent of the high Tg low dielectric active ester can be used for preparing high heat-resistant low dielectric laminated boards for electronic appliances, and the technical indexes are as follows: the dielectric constant is 3.79-3.95 at 10GHz, the dielectric loss is 0.0073-0.0085, the glass transition temperature (DMA method) is 217-247 ℃, the water absorption rate is 0.11-0.18%, the thermal decomposition temperature (5%) is 396-426 ℃, and the thermal delamination time T300 is more than 60 min.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the high Tg low-dielectric active ester curing agent contains two reaction groups of maleimide group and active ester group, can directly react with epoxy resin in a ring-opening manner, and simultaneously generates double bond crosslinking between the maleimide groups to form a crosslinked and dense three-dimensional network structure. Compared with the common active ester curing agent (only containing active ester groups), the cross-linking density of the epoxy resin curing can be improved, and the heat resistance of the laminated board is improved;
(2) by adopting the invention, the high Tg low dielectric active ester curing agent is applied to the preparation of the high heat-resistant low dielectric laminated board, the high Tg low dielectric active ester curing agent has the reaction characteristic of active ester and the reaction characteristic of bismaleimide resin, the performance characteristics of the active ester curing agent and the bismaleimide resin are integrated, and the prepared high heat-resistant low dielectric laminated board has good comprehensive performance, wherein: the dielectric constant is 3.79-3.95 at 10GHz, the dielectric loss is 0.0073-0.0085, the glass transition temperature (DMA method) is 217-247 ℃, the water absorption rate is 0.11-0.18%, the thermal decomposition temperature (5%) is 396-426 ℃, and the thermal delamination time T300 is more than 60 min;
(3) the product of the invention has simple preparation process, easy operation and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Preparation of the first part high Tg Low dielectric active ester curing agent
Example 1:
the preparation method of the high Tg low dielectric active ester curing agent comprises the following implementation steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.11-0.15 mol of maleic anhydride in 75-130 ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the (dissolved) maleic anhydride solution into the reactor A at a dropping speed of 1-2 ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 2-3 h after dropwise adding is finished; then adding 0.14-0.2 mol of acetic anhydride and 0.0001-0.0008 mol of catalyst, heating to 60-65 ℃, reacting for 3-4 h, cooling, precipitating with (a large amount of) water (which can be tap water, deionized water or distilled water), filtering, washing, and recrystallizing to prepare 5-maleimide-isophthalic acid;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 100-200 mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring and dissolving, dropwise adding 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dropwise adding is finished, slowly heating to 50-60 ℃, stirring for 2-3 h, and distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl dichloride;
c. mixing 0.1mol of aromatic phenol compound, 0.3 to 0.65mol of acid-binding agent, and 100 to 200mL of solvent C (solvent C)1) Adding the mixture into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; 0.025 to 0.2mol of 5-maleimido-isophthaloyl chloride, 0to 0.1mol of aromatic diacid chloride, and 200 to 500mL of solvent C (solvent C)2) And adding the mixture into a container E to prepare a diacylchloride solution, dropwise adding the diacylchloride solution into a reactor D at a dropping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dropwise adding, stirring for 2-3 h, adding 0.055-0.3 mol of monophenol compound, continuously stirring for 2-3 h, and carrying out filtering, alkali washing, water washing, extraction, distillation, drying and other steps to obtain the high-Tg low-dielectric-constant active ester curing agent of the embodiment 1-5.
The catalyst is sodium acetate or nickel acetate; the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone; the solvent B is toluene or xylene; the solvent C is toluene or xylene; the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the acid-binding agent is triethylamine or pyridine; the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
Table 1: examples 1-1 to 1-5 composition ratios and performance parameters of high Tg low dielectric active ester curatives:
application of second part of high-Tg low-dielectric active ester curing agent
Example 2:
the preparation method of the high heat-resistant low dielectric laminated board comprises the following implementation steps:
(1) uniformly mixing 100 parts by mass of epoxy resin, 65-160 parts by mass of a high Tg low dielectric active ester curing agent, 0.35-1.2 parts by mass of a curing accelerator, 30-110 parts by mass of an inorganic filler and a proper amount of a solvent to prepare a resin glue solution with a solid content of 60-70%, impregnating with 1080E glass fiber cloth, controlling the resin content to be 68%, and baking at 130-170 ℃ for 1-10 min to prepare a prepreg;
(2) stacking 10 prepregs, attaching copper foils on two sides, placing the prepregs in a vacuum hot press, heating the prepregs to 170 ℃ from room temperature at the heating rate of 3 ℃/min, heating the prepregs to 4MPa from 0.5MPa at the heating rate of 0.1MPa/1min, vacuumizing the prepregs to 50torr, keeping the prepregs in a pressed state for 2 hours, heating the prepregs to 200 ℃ for 2 hours at a constant pressure, heating the prepregs to 250 ℃ for hot pressing for 2 hours, releasing the pressure, naturally cooling the prepregs to 150 ℃, heating the prepregs to 260 ℃ again, heating the prepregs to 3MPa for pressing for 2 hours, releasing the pressure, and naturally cooling the prepregs to obtain the high-heat-resistance low-dielectric laminated board of the embodiment 2-1-2-6.
The raw materials used in the examples:
a1: SQCN703, Shengquan O-cresol formaldehyde epoxy resin, and the epoxy equivalent is 200-210 g/eq;
a2: SQPN638, Shengquan phenol novolac epoxy resin, and the epoxy equivalent is 170-190 g/eq;
a3: DPNE1501, Jiashengda dicyclopentadiene phenol type epoxy resin, 253 and 268g/eq of epoxy equivalent;
b1: the high Tg low dielectric active ester curative prepared in example 1-1;
b2: the high Tg low dielectric active ester curing agent prepared in examples 1-2;
b3: the high Tg low dielectric active ester curatives prepared in examples 1-3;
b4: the high Tg low dielectric active ester curatives prepared in examples 1-4;
b5: the high Tg low dielectric active ester curatives prepared in examples 1-5;
c1: 2-methylimidazole, formed in four countries;
c2: 2-ethyl-4-methylimidazole, formed in four countries;
d: silicon dioxide, Jiangsu birry DQ 1040;
e1: acetone;
e2: butanone;
table 2: the resin solution of the embodiment 2-1-2-5 comprises the following components in percentage by weight:
table 3: examples 2-1 to 2-8 tables of Properties of the high Heat resistant Low dielectric laminates:
comparative example of the third section
In the comparative example, aromatic diphenol, aromatic diacid chloride and monophenol compound are reacted according to the method of step c in example 1 to prepare polyester type active ester, then the polyester type active ester is mixed with epoxy resin, inorganic filler and other components to prepare resin glue solution, epoxy resin based prepreg and laminated board are prepared, and the preparation process of the glue solution, prepreg and laminated board is the same as that of the example and is not described differently.
Comparative example: preparation of polyester type active ester curing agent:
mixing 0.1mol of aromatic phenol compound, 0.3 to 0.65mol of acid-binding agent, and 100 to 200mL of solvent C (solvent C)1) Adding the mixture into a reactor F provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; mixing 0.125-0.2 mol of aromatic diacid chloride and 200-400 mL of solvent C (solvent C)2) Adding the mixture into a container G to prepare an aromatic diacyl chloride solution, then dropwise adding the aromatic diacyl chloride solution into a reactor F at a dropping speed of 0.5-1 ml/min, slowly heating to 50-65 ℃ after dropwise adding, stirring for 2-3 h, then adding 0.055-0.3 mol of monophenol compound, continuously stirring for 2-3 h, and carrying out filtering, alkali washing, water washing, extraction, distillation, drying and other steps to obtain the conventional polyester type active ester curing agent of comparative examples 3-1-3-5.
The solvent C is toluene or xylene; the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the acid-binding agent is triethylamine or pyridine; the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
Table 4: comparative examples 3-1 to 3-5 composition ratios and performance parameters of polyester type active ester curing agents are shown in the following table:
comparative examples 4-1 to 4-5 used raw materials:
a1: SQCN703, Shengquan O-cresol formaldehyde epoxy resin, and the epoxy equivalent is 200-210 g/eq;
a2: SQPN638, Shengquan phenol novolac epoxy resin, and the epoxy equivalent is 170-190 g/eq;
a3: DPNE1501, Jiashengda dicyclopentadiene phenol type epoxy resin, 253 and 268g/eq of epoxy equivalent; b6: the polyester type active ester curing agent prepared in comparative example 1-1;
b7: the polyester type active ester curing agent prepared in comparative example 1-2;
b8: polyester-type active ester curing agent prepared in comparative examples 1 to 3;
b9: polyester-type active ester curing agents prepared in comparative examples 1 to 4;
b10: polyester-type active ester curing agents prepared in comparative examples 1 to 5;
c1: 2-methylimidazole, formed in four countries;
c2: 2-ethyl-4-methylimidazole, formed in four countries;
d: silicon dioxide, Jiangsu birry DQ 1040;
e1: acetone; e2: butanone;
table 5: comparative examples 4-1 to 4-5 resin solution components and ratios:
table 6: comparative examples 4-1 to 4-5 epoxy resin-based laminates:
example 5:
a high Tg low dielectric active ester curing agent has a chemical structural general formula shown in (I):
in formula (I): m is 0-4, n is 0-4, and the sum of m and n is 0-8; r1Is composed of
Any one of (a); r2Is composed of
R3Is composed of
Any of the above.
The high Tg low dielectric active ester curing agent is yellow powder, the softening point is 126-149 ℃, and the ester equivalent weight is 187-245 g/eq.
Example 6:
a preparation method of a high Tg low dielectric active ester curing agent comprises the following steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.11mol of maleic anhydride in 75ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the (dissolved) maleic anhydride solution into the reactor A at a dropping speed of 1ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 3 hours after dropwise adding is finished; then adding 0.14mol of acetic anhydride and 0.0001mol of catalyst, heating to 60 ℃, reacting for 4 hours, cooling, precipitating with (a large amount of) water (which can be tap water, deionized water or distilled water), filtering, washing, and recrystallizing to obtain 5-maleimide-isophthalic acid;
the catalyst is sodium acetate or nickel acetate;
the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 100mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring for dissolving, dropwise adding 0.23mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 1mL/min under the condition of ice-water bath, continuously stirring for 2h after dropwise adding is finished, slowly raising the temperature to 50 ℃, stirring for 3h, distilling, concentrating and drying to prepare 5-maleimide-isophthaloyl chloride;
the solvent B is toluene or xylene;
c. adding 0.1mol of aromatic phenol compound, 0.3mol of acid-binding agent and 100mL of solvent C into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; adding 0.025mol of 5-maleimide-isophthaloyl dichloride and 200mL of solvent C into a container E to prepare a diacyl chloride solution, then dropwise adding the diacyl chloride solution into a reactor D at a dropping speed of 0.5mL/min, slowly heating to 50 ℃ after dropwise adding, stirring for 3h, then adding 0.055mol of monophenol compound, continuously stirring for 3h, and filtering, alkali washing, water washing, extracting, distilling, drying (and the like) to obtain the high Tg low dielectric active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane;
the acid-binding agent is triethylamine or pyridine;
the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
Example 7:
a preparation method of a high Tg low dielectric active ester curing agent comprises the following steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.15mol of maleic anhydride in 130ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the (dissolved) maleic anhydride solution into the reactor A at a dropping speed of 2ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 2 hours after dropwise adding is finished; then adding 0.2mol of acetic anhydride and 0.0008mol of catalyst, heating to 65 ℃, reacting for 3 hours, cooling, precipitating with (a large amount of) water (which can be tap water, deionized water or distilled water), filtering, washing, and recrystallizing to obtain 5-maleimide-isophthalic acid;
the catalyst is sodium acetate or nickel acetate;
the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 200mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring and dissolving, dripping 4mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 3mL/min under the condition of ice-water bath, continuing stirring for 1h after dripping is finished, slowly heating to 60 ℃, stirring for 2, and distilling, concentrating and drying to prepare 5-maleimide-isophthaloyl chloride;
the solvent B is toluene or xylene;
c. adding 0.1mol of aromatic phenol compound, 0.65mol of acid-binding agent and 200mL of solvent C into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; adding 0.2mol of 5-maleimide-isophthaloyl chloride and 500mL of solvent C into a container E to prepare a diacyl chloride solution, then dropwise adding the diacyl chloride solution into a reactor D at a dropping speed of 1mL/min, slowly heating to 65 ℃ after dropwise adding, stirring for 2h, then adding 0.3mol of monophenol compound, continuously stirring for 2h, and obtaining the high-Tg low-dielectric-constant active ester curing agent through the steps of filtering, alkali washing, water washing, extracting, distilling, drying and the like;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane;
the acid-binding agent is triethylamine or pyridine;
the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
Example 8:
a preparation method of a high Tg low dielectric active ester curing agent comprises the following steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.13mol of maleic anhydride in 100ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the (dissolved) maleic anhydride solution into the reactor A at a dropping speed of 2ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 2.5 hours after dropwise adding is finished; then adding 0.17mol of acetic anhydride and 0.0005mol of catalyst, heating to 63 ℃, reacting for 3.5h, cooling, precipitating with (a large amount of) water (which can be tap water, deionized water or distilled water), filtering, washing, and recrystallizing to obtain 5-maleimide-isophthalic acid;
the catalyst is sodium acetate or nickel acetate;
the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 150mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring for dissolving, dropwise adding 0.32mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 3mL/min under the condition of ice-water bath, continuously stirring for 1.5h after dropwise adding is finished, slowly raising the temperature to 55 ℃, stirring for 2.5h, distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl dichloride;
the solvent B is toluene or xylene;
c. adding 0.1mol of aromatic phenol compound, 0.48mol of acid-binding agent and 150mL of solvent C into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; adding 0.11mol of 5-maleimide-isophthaloyl dichloride and 350mL of solvent C into a container E to prepare a diacyl chloride solution, then dropwise adding the diacyl chloride solution into a reactor D at a dropping speed of 1mL/min, slowly heating to 58 ℃ after dropwise adding, stirring for 2.5h, then adding 0.16mol of monophenol compound, continuously stirring for 2.5h, and carrying out filtration, alkali washing, water washing, extraction, distillation, drying (and other steps) to obtain the high-Tg low-dielectric-activity ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane;
the acid-binding agent is triethylamine or pyridine;
the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
Example 9:
in the step c, 0.1mol of aromatic diacid chloride is also added into the diacid chloride solution; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the rest of the procedures are the same as those in examples 6 to 8, and are omitted.
Example 10:
in the step c, 0.01mol of aromatic diacid chloride is also added into the diacid chloride solution; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the rest of the procedures are the same as those in examples 6 to 8, and are omitted.
Example 11:
in the step c, 0.05mol of aromatic diacid chloride is also added into the diacid chloride solution; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the rest of the procedures are the same as those in examples 6 to 8, and are omitted.
Example 12:
the high Tg low dielectric active ester curing agent can be used for preparing high heat-resistant low dielectric laminated boards for electronic appliances, and the technical indexes are as follows: the dielectric constant is 3.79-3.95 at 10GHz, the dielectric loss is 0.0073-0.0085, the glass transition temperature (DMA method) is 217-247 ℃, the water absorption rate is 0.11-0.18%, the thermal decomposition temperature (5%) is 396-426 ℃, and the thermal delamination time T300 is more than 60 min.
The relevant criteria used for the technical indicators herein are as follows:
glass transition temperature Tg: measured by dynamic thermomechanical analysis (DMA) according to the DMA method defined by IPC-TM-650, 2.4.24.4;
dielectric constant Dk and dielectric loss Df: testing 10GHz data by adopting an SPDR method according to a method specified by IEC 61189-2-721;
water absorption: measured according to the method defined in IPC-TM-650 at 2.6.2.1;
thermal stratification time T300: measured according to the method defined in IPC-TM-650 at 2.4.24.1;
5% thermal weight loss temperature (Td 5%): the measurement was carried out according to the method defined in IPC-TM-650, 2.4.24.6.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, concentration, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (4)
1. A high Tg low dielectric active ester curing agent is characterized in that: the high Tg low dielectric active ester curing agent has a chemical structural general formula shown in (I):
in formula (I): m is 0-4, n is 0-4, and the sum of m and n is 0-8; r1Is composed of
Any one of (a); r2Is composed of
R3Is composed of
Any of the above.
2. A preparation method of a high Tg low dielectric active ester curing agent is characterized by comprising the following steps:
a. adding 0.1mol of 3, 5-dicarboxylic aniline and 75ml of solvent A into a reactor A provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and stirring for dissolving; dissolving 0.11-0.15 mol of maleic anhydride in 75-130 ml of solvent A in a container B to prepare a maleic anhydride solution; dropwise adding the maleic anhydride solution into the reactor A at a dropping speed of 1-2 ml/min through a constant-pressure dropping funnel under the condition of water bath, and continuously stirring for 2-3 h after dropwise adding is finished; then adding 0.14-0.2 mol of acetic anhydride and 0.0001-0.0008 mol of catalyst, heating to 60-65 ℃, reacting for 3-4 h, cooling, precipitating with water, filtering, washing, and recrystallizing to obtain 5-maleimide-isophthalic acid;
the catalyst is sodium acetate or nickel acetate;
the solvent A is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;
b. adding 0.1mol of 5-maleimide-isophthalic acid and 100-200 mL of solvent B into a reactor C provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring and dissolving, dropwise adding 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel according to 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dropwise adding is finished, heating to 50-60 ℃, stirring for 2-3 h, distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl dichloride;
the solvent B is toluene or xylene;
c. adding 0.1mol of aromatic phenol compound, 0.3-0.65 mol of acid-binding agent and 100-200 mL of solvent C into a reactor D provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirring for dissolving; adding 0.025-0.2 mol of 5-maleimide-isophthaloyl dichloride, 0-0.1 mol of aromatic diacid chloride and 200-500 mL of solvent C into a container E to prepare a diacid chloride solution, then dropwise adding the solution into a reactor D at a dropping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dropwise adding, stirring for 2-3 h, then adding 0.055-0.3 mol of monophenol compound, continuously stirring for 2-3 h, and filtering, alkali washing, water washing, extracting, distilling and drying to obtain the high Tg low dielectric constant active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of bisphenol S, bisphenol A, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 2, 6-naphthalenediol, 4' -biphenyldiphenol, 2 ' -biphenyldiphenol, dicyclopentadiene type phenol, 2 ' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylmethane, 2, 4' -dihydroxydiphenylmethane, and 2,2 ' -dihydroxy-3, 3 ' -dimethyldiphenylmethane;
the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride;
the acid-binding agent is triethylamine or pyridine;
the monophenol compound is any one of phenol, 1-naphthol, 2-naphthol, p-hydroxybiphenyl and biphenyl-2-ol.
3. The method for preparing the high Tg low dielectric active ester curing agent as claimed in claim 2, wherein the method comprises the following steps: in the step c, 0to 0.1mol of the aromatic diacid chloride is replaced by 0.01 to 0.1mol of the aromatic diacid chloride.
4. The application of the high Tg low dielectric active ester curing agent is characterized in that: the high Tg low dielectric active ester curing agent is used for preparing high heat-resistant low dielectric laminated boards for electronic and electric appliances.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694451A (en) * | 2020-12-24 | 2021-04-23 | 广东盈骅新材料科技有限公司 | Modified allyl compound, bismaleimide prepolymer and application thereof |
| CN115819317A (en) * | 2022-12-27 | 2023-03-21 | 苏州生益科技有限公司 | Active ester compound and resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979393A (en) * | 1973-12-20 | 1976-09-07 | Ciba-Geigy Corporation | Imidyl- and isoimidyl-phthalic anhydrides, process for their manufacture and their use for curing epoxide resins |
| WO2017170551A1 (en) * | 2016-03-29 | 2017-10-05 | 日本化薬株式会社 | Maleimide resin, curable resin composition and cured product of same |
| CN110655791A (en) * | 2019-09-30 | 2020-01-07 | 艾蒙特成都新材料科技有限公司 | High heat-resistant low-dielectric active ester resin composition and preparation method of laminated board |
| CN111777751A (en) * | 2020-06-30 | 2020-10-16 | 艾蒙特成都新材料科技有限公司 | high-Tg low-dielectric self-crosslinking active ester curing agent and preparation method and application thereof |
| US20210032383A1 (en) * | 2018-03-29 | 2021-02-04 | Dic Corporation | Curable composition and cured product thereof |
-
2020
- 2020-06-30 CN CN202010611742.3A patent/CN111777541B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979393A (en) * | 1973-12-20 | 1976-09-07 | Ciba-Geigy Corporation | Imidyl- and isoimidyl-phthalic anhydrides, process for their manufacture and their use for curing epoxide resins |
| WO2017170551A1 (en) * | 2016-03-29 | 2017-10-05 | 日本化薬株式会社 | Maleimide resin, curable resin composition and cured product of same |
| US20210032383A1 (en) * | 2018-03-29 | 2021-02-04 | Dic Corporation | Curable composition and cured product thereof |
| CN110655791A (en) * | 2019-09-30 | 2020-01-07 | 艾蒙特成都新材料科技有限公司 | High heat-resistant low-dielectric active ester resin composition and preparation method of laminated board |
| CN111777751A (en) * | 2020-06-30 | 2020-10-16 | 艾蒙特成都新材料科技有限公司 | high-Tg low-dielectric self-crosslinking active ester curing agent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAOYU TAN，等: "Synthesis, preparation and properties of novel high-performance allyl–maleimide resins", 《POLYMER》 * |
| 张文利等: "6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并？嗪及其共聚物的合成", 《高等学校化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694451A (en) * | 2020-12-24 | 2021-04-23 | 广东盈骅新材料科技有限公司 | Modified allyl compound, bismaleimide prepolymer and application thereof |
| CN112694451B (en) * | 2020-12-24 | 2023-03-07 | 广东盈骅新材料科技有限公司 | Modified allyl compound, bismaleimide prepolymer and application thereof |
| CN115819317A (en) * | 2022-12-27 | 2023-03-21 | 苏州生益科技有限公司 | Active ester compound and resin composition |
| CN115819317B (en) * | 2022-12-27 | 2024-03-08 | 苏州生益科技有限公司 | Active ester compound and resin composition |
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