CN111777751B - high-Tg low-dielectric self-crosslinking active ester curing agent and preparation method and application thereof - Google Patents
high-Tg low-dielectric self-crosslinking active ester curing agent and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
- 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
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Abstract
The invention discloses a high Tg low dielectric self-crosslinking active ester curing agent and a preparation method thereof, wherein the preparation method of the compound comprises the following steps: reacting dicarboxylic acid aniline, maleic anhydride, acetic anhydride and a catalyst to obtain 5-maleimide-isophthalic acid; reacting 5-maleimide-isophthalic acid and thionyl chloride to obtain 5-maleimide-isophthaloyl dichloride; adding an aromatic phenol compound, an acid-binding agent and a solvent into a reactor, stirring and dissolving; mixing maleimide-isophthaloyl dichloride, aromatic diacid chloride and a solvent to prepare a diacid chloride solution, dropwise adding the diacid chloride solution into a reactor, heating the solution to react under stirring, adding a monophenol compound to react under stirring, filtering, washing, extracting, distilling, drying and the like to obtain the compound. The high-Tg low-dielectric self-crosslinking 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 self-crosslinking active ester curing agent and a preparation method and application thereof. The low-dielectric self-crosslinking 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 the base material of the printed circuit board, the epoxy resin has wide application due to good manufacturability and comprehensive performance, however, the traditional epoxy resin-based laminated board generally adopts amines, linear phenolic resin, acid anhydride and the like as curing agents, and the 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 ℃ (field courage, piBrassica, etc.. Polyphenylene oxide/epoxy resin system [ J ] for high-performance copper clad laminate 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 the molecular chain of the cured epoxy resin and improve the dielectric property of the epoxy resin-based laminated board, however, the glass heat resistance of the laminated board is often damaged by the ester-based side chain with plasticizing effect, 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', 2' -tetraphenylethane active ester curing agent and benzoxazine to form the resin composition, wherein the 1,1', 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' -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 self-crosslinking active ester curing agent, and a preparation method and application thereof. The high Tg low-dielectric self-crosslinking active ester curing agent provided by the invention is polyester active ester with maleimide groups and allyl groups, can enable epoxy resin to carry out ring-opening reaction, and simultaneously, double bond crosslinking reaction is carried out between the maleimide groups and the allyl groups, so that a crosslinking network structure similar to a bismaleimide resin, epoxy resin and diallyl bisphenol A system is directly formed, the crosslinking density of a cured product is improved, the aim of improving the heat resistance of an active ester cured epoxy resin-based laminated board is fulfilled, and the laminated board is endowed with excellent dielectric properties.
The content of the invention is as follows: a self-crosslinking active ester curing agent with high Tg and low dielectric constant is characterized in that: the high Tg low-dielectric self-crosslinking active ester curing agent has a chemical structural general formula shown in (I):
in the formula (I): m = 0-4,n = 0-4,m and n sum is 0-8; r is 1 Is composed of
Any one of (a); r is 2 Is composed of
R 3 Is composed of
Any one of them.
The high Tg low-dielectric self-crosslinking active ester curing agent is yellow powder, the number average molecular weight is 947-2716, the molecular weight distribution index is 1.28-1.81, the softening point is 104-121 ℃, and the ester equivalent is 149-265 g/eq.
Another aspect of the invention is: a preparation method of a self-crosslinking active ester curing agent with high Tg and low dielectric constant 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; dripping the (dissolved) maleic anhydride solution into the reactor A through a constant-pressure dropping funnel at a dropping speed of 1-2 mL/min under the condition of water bath, and continuously stirring for 2-3 h after dripping 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, dropping 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel at a dropping speed of 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dropping is finished, slowly heating to 50-60 ℃, stirring for 2-3 h, distilling, concentrating and drying to prepare 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; mixing 0.025-0.2 mol of 5-maleimide-isophthaloyl dichloride, 0-0.1 mol of aromatic diacid chloride and 200-550 mL of solvent C in a container E to prepare diacid chloride solution, then dripping the solution into a reactor D at the dripping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dripping, 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, drying (and the like) to obtain the high Tg low-dielectric self-crosslinking type active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol;
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: the aromatic diacid chloride of 0to 0.1mol can be replaced by the aromatic diacid chloride of 0.01 to 0.1mol.
Another aspect of the invention is: the application of the self-crosslinking active ester curing agent with high Tg and low dielectric constant is characterized in that: the self-crosslinking active ester curing agent can be used for preparing high-heat-resistance low-dielectric laminated boards for electronic appliances, and has the technical indexes that: the dielectric constant is 3.81-3.92 at 10GHz, the dielectric loss is 0.008-0.009, the glass transition temperature (DMA method) is 225-254 ℃, the water absorption is 0.12-0.2%, the thermal decomposition temperature (5%) is 405-429 ℃, and the thermal delamination time T300 is more than 60min.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) The high Tg low-dielectric self-crosslinking active ester curing agent contains three reactive groups of maleimide group, active ester group and allyl group, can directly react with epoxy resin in a ring-opening manner, and simultaneously generates double bond crosslinking reaction among the maleimide groups and the allyl groups, thereby simplifying the step of modifying bismaleimide by an allyl compound and directly forming a crosslinking network structure similar to a bismaleimide resin, an epoxy resin and a diallyl bisphenol A system. 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 resin cured product is improved;
(2) By adopting the invention, the high Tg low dielectric self-crosslinking active ester curing agent is applied to the preparation of the high heat-resistant low dielectric laminated board, the active ester curing agent has the reaction characteristic of active ester and the reaction characteristic of allyl phenol compound modified bismaleimide resin, the performance characteristics of the active ester curing agent and the allyl phenol compound modified bismaleimide resin are integrated, and the prepared high heat-resistant low dielectric laminated board has good comprehensive performance, wherein: dielectric constant of 3.81-3.92 at 10GHz, dielectric loss of 0.008-0.009, glass transition temperature (DMA method) of 225-254 ℃, water absorption of 0.12-0.2%, thermal decomposition temperature (5%) of 405-429 ℃, and thermal stratification time T300 of more than 60min;
(3) The product of the invention has simple preparation process, easy operation and strong practicability.
Detailed Description
The following examples are given to further illustrate the present invention and are not to 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 maleic anhydride solution; dripping the (dissolved) maleic anhydride solution into the reactor A through a constant-pressure dropping funnel at a dropping speed of 1-2 ml/min under the condition of water bath, and continuously stirring for 2-3 h after the dripping 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 obtain 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, dripping 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel at a dripping speed of 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dripping is finished, slowly heating to 50-60 ℃, stirring for 2-3 h, distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl chloride;
c. 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-maleimide-isophthaloyl chloride, 0to 0.1mol of aromatic diacid chloride and 200 to 550mL of solvent C (solvent C) 2 ) Mixing in a container E to prepare a diacyl chloride solution, then dripping into a reactor D at the dripping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dripping is finished, stirring for 2-3 h, then adding 0.055-0.3 mol of monophenol compound, continuously stirring for 2-3 h, and carrying out the steps of filtering, alkali washing, water washing, extracting, distilling, drying and the like to obtain the self-crosslinking active ester curing agent with high Tg and low dielectric constant 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 diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol; 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 the high Tg low dielectric self-crosslinking active ester curatives are given in the table:
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, 55-173 parts by mass of high-Tg low-dielectric self-crosslinking active ester curing agent, 0.5-1.5 parts by mass of curing accelerator, 35-110 parts by mass of inorganic filler and a proper amount of 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, with an epoxy equivalent of 200-210 g/eq;
a2: SQPN638, shengquan phenol novolac epoxy resin, epoxy equivalent 170-190 g/eq;
a3: DPNE1501, jiashengda dicyclopentadiene phenol type epoxy resin, the epoxy equivalent is 253 to 268g/eq;
b1: the high Tg low dielectric self-crosslinking type active ester curative prepared in example 1-1;
b2: the high Tg low dielectric self-crosslinking type active ester curing agent prepared in example 1-2;
b3: the high Tg low dielectric self-crosslinking reactive ester curatives prepared in examples 1-3;
b4: the high Tg low dielectric self-crosslinking type active ester curatives prepared in examples 1-4;
b5: the high Tg low dielectric self-crosslinking reactive 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 DQ1040;
e1: acetone;
e2: butanone;
table 2: the resin solution of examples 2-1 to 2-5 comprises the following components in percentage by weight:
table 3: examples 2-1 to 2-8 Table of Properties of the high Heat resistant Low dielectric laminates:
comparative example of the third section
In comparative examples 3-1 to 3-5, aromatic diphenol, aromatic diacid chloride and monophenol compound were reacted according to the method of step c in example 1 to obtain a conventional polyester type active ester, comparative examples 3 to 6 were diallyl bisphenol a modified bismaleimide resin, the product obtained in the above comparative examples was mixed with epoxy resin, inorganic filler and other components to prepare a resin paste, and epoxy resin based prepregs and laminates were prepared; the preparation processes of the glue solution, the prepreg and the laminated board are the same as those of the embodiment, and no difference is made.
Comparative examples 3-1 to 3-5: preparation of conventional polyester type active ester curing agent:
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; 0.125 to 0.2mol of aromatic diacid chloride and 200 to 400mL of solvent C (solvent C) 2 ) Adding the mixture into a container G to prepare a diacyl chloride solution, then dropwise adding the solution into a reactor F at the 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 the steps of filtering, alkali washing, water washing, extracting, distilling, drying and the like to obtain the conventional polyester type 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' -biphenyldiol, 2' -biphenyldiol, 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.
Comparative examples 3 to 6: 40 parts by mass of diallyl bisphenol A (DABPA) and 100 parts by mass of N, N-4,4' -diphenylmethane bismaleimide resin (New bismaleimide Co., ltd., honghu) were added to a 250ml three-neck flask, and the temperature of the oil bath was slowly raised to 130 ℃, kept stirring and reacted at a constant temperature for 90min, and then cooled to room temperature to obtain the diallyl bisphenol A modified bismaleimide prepolymer of comparative example 3-6.
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 4-6 used raw materials:
a1: SQCN703, shengquan O-cresol formaldehyde epoxy resin, with the epoxy equivalent of 200-210 g/eq;
a2: SQPN638, shengquan phenol novolac epoxy resin, epoxy equivalent 170-190 g/eq;
a3: DPNE1501, jiashengda dicyclopentadiene phenol type epoxy resin, the epoxy equivalent 253-268g/eq;
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;
b11: diallyl bisphenol A-modified bismaleimide prepolymer 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 DQ1040;
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 self-crosslinking active ester curing agent has a chemical structural general formula shown in (I):
in the formula (I): m = 0-4,n = 0-4,m and n sum is 0-8; r 1 Is composed of
Any one of (a); r 2 Is composed of
R 3 Is composed of
Any of the above.
The high Tg low dielectric self-crosslinking active ester curing agent is yellow powder, the softening point is 102-121 ℃, and the ester equivalent is 149-265 g/eq.
Example 6:
a preparation method of a high Tg low dielectric self-crosslinking 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, recrystallizing, and preparing 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 at the dropping speed of 1mL/min under the condition of ice-water bath, continuing stirring for 2 hours after dropwise adding is finished, slowly heating to 50 ℃, stirring for 3 hours, 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; mixing 0.025mol of 5-maleimide-isophthaloyl chloride and 200mL of solvent C in 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 is finished, stirring for 3h, then adding 0.055mol of monophenol compound, continuously stirring for 3h, and filtering, alkali washing, water washing, extracting, distilling and drying (and other steps) to obtain the high Tg low-dielectric self-crosslinking active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol;
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 self-crosslinking 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 for dissolving, dripping 0.4mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel at the dropping speed of 3mL/min under the condition of ice-water bath, continuing stirring for 1h after dripping is finished, slowly heating to 60 ℃, stirring for 2h, 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; mixing 0.2mol of 5-maleimide-isophthaloyl chloride and 550mL of solvent C in 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 2 hours, then adding 0.3mol of monophenol compound, continuously stirring for 2 hours, and filtering, alkali washing, water washing, extracting, distilling, drying (and the like) to obtain the high Tg low-dielectric self-crosslinking type active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol;
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 self-crosslinking 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 2.5h after dropwise adding is finished; then adding 0.17mol of acetic anhydride and 0.0004mol 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, dripping 0.33mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel at the dropping speed of 2mL/min under the condition of ice-water bath, continuing stirring for 1.5 hours after dripping is finished, slowly heating to 55 ℃, stirring for 2.5 hours, distilling, concentrating and drying to obtain 5-maleimide-isophthaloyl chloride;
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; mixing 0.11mol of 5-maleimide-isophthaloyl chloride and 380mL of solvent C in 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 2.5 hours, then adding 0.16mol of monophenol compound, continuously stirring for 2.5 hours, and filtering, alkali washing, water washing, extracting, distilling, drying (and the like) to obtain the high Tg low dielectric self-crosslinking type active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol;
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:
a preparation method of a high Tg low dielectric self-crosslinking active ester curing agent, wherein 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:
a preparation method of a self-crosslinking active ester curing agent with high Tg and low dielectric constant, wherein 0.01mol of aromatic diacid chloride is also added into the diacid chloride solution in the step c; 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:
a preparation method of a self-crosslinking active ester curing agent with high Tg and low dielectric constant, wherein 0.05mol of aromatic diacid chloride is also added into the diacid chloride solution in the step c; the aromatic diacid chloride is isophthaloyl dichloride or terephthaloyl dichloride; the other examples are the same as examples 6 to 8, and are omitted.
Example 12:
the self-crosslinking active ester curing agent can be used for preparing high-heat-resistance low-dielectric laminated boards for electronic appliances, and the technical indexes are as follows: the dielectric constant is 3.81-3.92 at 10GHz, the dielectric loss is 0.008-0.009, the glass transition temperature (DMA method) is 225-254 ℃, the water absorption rate is 0.12-0.2 percent, the thermal decomposition temperature (5 percent) is 405-429 ℃, and the thermal stratification time T300 is more than 60min.
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 specified in 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 specified in IPC-TM-650, 2.6.2.1;
thermal stratification time T300: measured according to the method specified in IPC-TM-650, 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 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 self-crosslinking active ester curing agent is characterized in that: the high Tg low-dielectric self-crosslinking active ester curing agent has a chemical structural general formula shown in (I):
in formula (I): m = 0-4,n = 0-4,m and n sum is 0-8; r 1 Is composed of
Any one of (a) to (b); r 2 Is composed of
R 3 Is composed of
Any of the above.
2. A preparation method of a self-crosslinking active ester curing agent with high Tg and low dielectric constant 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; dripping the maleic anhydride solution into the reactor A at a dripping 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 dripping; 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 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, dripping 0.23-0.4 mol of thionyl chloride into the reactor C through the constant-pressure dropping funnel at a dripping speed of 1-3 mL/min under the condition of ice-water bath, continuously stirring for 1-2 h after dripping is finished, slowly heating to 50-60 ℃, stirring for 2-3 h, 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, 0.3-0.65 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; mixing 0.025-0.2 mol of 5-maleimide-isophthaloyl chloride, 0-0.1 mol of aromatic diacid chloride and 200-550 mL of solvent C in a container E to prepare a diacid chloride solution, then dripping the solution into a reactor D at the dripping speed of 0.5-1 mL/min, slowly heating to 50-65 ℃ after dripping is finished, 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 self-crosslinking active ester curing agent;
the solvent C is toluene or xylene;
the aromatic phenol compound is any one of diallyl bisphenol A, diallyl bisphenol S, 2, 5-allyl-p-phenol, 2, 6-allyl-1, 5-naphthalenediol, 3 '-diallyl-4, 4' -dihydroxy diphenylmethane and o-allyl DCPD phenol;
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 self-crosslinking active ester curing agent with high Tg and low dielectric constant as claimed in claim 2, which is characterized in that: the content of the aromatic diacid chloride is 0.01 to 0.1mol.
4. The use of the self-crosslinking active ester curing agent with high Tg and low dielectric constant of claim 1, wherein: the self-crosslinking active ester curing agent is used for preparing high-heat-resistance low-dielectric laminated plates for electronic and electric appliances.
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| 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 |
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| 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 |
| CN111018769A (en) * | 2019-12-26 | 2020-04-17 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance bismaleimide resin, preparation method and application |
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