Phosphorus-containing compound and manufacturing method thereof, resin composition comprising the same and article made therefrom

Abstract

This invention relates to a phosphorus-containing compound and a method for preparing the same, the phosphorus-containing compound comprising the structure shown in formula (1): Formula (1) In formula (1), X1-X3 are each independently a covalent bond, a C1-C5 alkylene group, a C2-C5 alkenyl group, a C2-C5 alkyne group, or -O-, R1-R6 are each independently a C1-C5 alkyl group, n1-n3 are each independently an integer from 0 to 3, and n4-n6 are each independently an integer from 0 to 4. Furthermore, this invention also relates to a resin composition comprising the aforementioned phosphorus-containing compound and a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, and articles made using said resin composition, including prepregs, resin films, laminates, or printed circuit boards, wherein at least one of the following properties of said articles is improved: glass transition temperature, stiffness, storage modulus loss rate, coefficient of thermal expansion, and curl flexibility.

Claims

1. A phosphorus-containing compound, characterized in that it comprises the structure shown in formula (1): In formula (1), X1-X3 are each independently covalently bonded, C1-C5 alkylene group, C2-C5 alkenyl group, C2-C5 alkyne group or -O-, R1-R6 are each independently C1-C5 alkyl group, n1-n3 are each independently an integer from 0 to 3, and n4-n6 are each independently an integer from 0 to 4.

2. The phosphorus-containing compound as claimed in claim 1, characterized in that it comprises any one or a combination of phosphorus-containing compounds of formulas (1-1) to (1-5): Formula (1-1) Formula (1-2) Formula (1-3) Formula (1-4) Formula (1-5).

3. A method for preparing a phosphorus-containing compound as claimed in claim 1, characterized in that, when X1-X3 in formula (1) are each independently a covalent bond or a C1-C5 alkylene group, the method comprises: Step 1: First, mix magnesium, iodine, and solvent to activate the magnesium. Then, add the compound shown in formula (2) to react and obtain the intermediate product; in formula (2), ... X4 is a covalent bond or a C1-C5 alkylene group, R7-R8 are each independently a C1-C5 alkyl group, n7 is an integer from 0 to 3, n8 is an integer from 0 to 4, and Br represents a bromine atom; Step 2: Add phosphorus trihalide to the intermediate product to carry out a substitution reaction to obtain the phosphorus-containing compound.

4. The preparation method as described in claim 3, characterized in that the activation temperature in step one is 40-60℃ and the time is 1-2 hours, the reaction temperature after the addition of the compound shown in formula (2) is 40-60℃ and the time is 6-10 hours; the substitution reaction temperature in step two is 20-30℃ and the time is 6-10 hours.

5. A method for preparing a phosphorus-containing compound as claimed in claim 1, characterized in that, when X1-X3 in formula (1) are each independently a C2-C5 alkenyl group, the method comprises: In a reactor, the compound shown in formula (3), catalyst, acid-binding agent, compound shown in formula (2), and solvent are added, and the temperature is raised to 90-110℃ and reacted for 8-12 hours to obtain the phosphorus-containing compound: Formula (3) In formula (3), X5 is a C1-C4 alkylene group; Formula (2) In formula (2), X4 is a covalent bond or a C1-C5 alkylene group, R7-R8 are each independently a C1-C5 alkyl group, n7 is an integer from 0 to 3, n8 is an integer from 0 to 4, and Br represents a bromine atom.

6. A method for preparing a phosphorus-containing compound as claimed in claim 1, characterized in that, when X1-X3 in formula (1) are each independently -O-, the method comprises: In a reactor, the compound shown in formula (4), an acid-binding agent, a solvent and phosphorus trihalide are added, and the temperature is raised to 90-110℃ and reacted for 5-7 hours to obtain the phosphorus-containing compound: formula (4). In formula (4), R9-R10 are each independently C1-C5 alkyl groups, n9 is an integer from 0 to 3, and n10 is an integer from 0 to 4.

7. A method for preparing a phosphorus-containing compound as claimed in claim 1, characterized in that, when X1-X3 in formula (1) are each independently a C2-C5 alkyne group, the method comprises: In a reactor, the compound shown in formula (5), catalyst, acid-binding agent, compound shown in formula (2), and solvent are added, and the temperature is raised to 50-110℃ and reacted for 8-12 hours to obtain the phosphorus-containing compound: Formula (5) In formula (5), X6 is a C1-C4 alkylene group; Formula (2) In formula (2), X4 is a covalent bond or a C1-C5 alkylene group, R7-R8 are each independently a C1-C5 alkyl group, n7 is an integer from 0 to 3, n8 is an integer from 0 to 4, and Br represents a bromine atom.

8. A resin composition, characterized in that it comprises a phosphorus-containing compound as described in claim 1 and a polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

9. The resin composition of claim 8, characterized in that the phosphorus-containing compound is in the form of 20-100 parts by weight relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

10. The resin composition of claim 8, characterized in that the phosphorus-containing compound comprises 30-80 parts by weight relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

11. The resin composition of claim 8, characterized in that the polyphenylene ether resin containing unsaturated carbon-carbon double bonds comprises any one or a combination of vinyl benzyl polyphenylene ether resin, (meth)acrylic polyphenylene ether resin, vinyl polyphenylene ether resin, allyl polyphenylene ether resin.

12. The resin composition of claim 8, characterized in that it further comprises any one or a combination thereof of a crosslinking agent containing unsaturated carbon-carbon double bonds, an organosilicon resin, a benzo[a]pyrene resin, an epoxy resin, a polyester resin, a phenolic resin, an amine curing agent, polyamide, polyimide, styrene-maleic anhydride, and cyanate ester resin.

13. The resin composition as claimed in claim 8, characterized in that it further comprises any one or a combination of a curing accelerator, a polymerization inhibitor, a flame retardant different from the phosphorus-containing compound shown in formula (1), an inorganic filler, a surface treatment agent, a dye, a toughening agent, and a solvent.

14. An article made from a resin composition as described in any one of claims 8 to 13, characterized in that it comprises a prepreg, a resin film, a laminate, or a printed circuit board.

15. The article of claim 14, characterized in that it has one or more of the following characteristics: a glass transition temperature greater than or equal to 244°C as determined by the method described in IPC-TM-650 2.4.24.4; a stiffness greater than or equal to 32648 N / m as determined by the method described in IPC-TM-650 2.4.24.4; a storage modulus loss rate less than or equal to 27.1% as determined by the method described in IPC-TM-650 2.4.24.4; a Z-axis coefficient of thermal expansion less than or equal to 108 ppm / °C as determined by the method described in IPC-TM-650 2.4.24; and a curling flexibility of grade 2-4.

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