Flame-retardant engineering plastic and preparation method thereof

Abstract

The present invention provides a flame-retardant engineering plastic and a preparation method thereof. The flame-retardant engineering plastic contains a halogen-free flame retardant represented by the formula I as a component of raw materials. The addition of the flame retardant gives good flame retardancy and excellent mechanical properties to the engineered plastic. The engineering plastic is prepared by the raw materials comprising the following components in parts by mass: 40-60 parts of PC, 20-40 parts of epoxy resin, 10-20 parts of ABS and 5-15 parts of flame retardant. The engineering plastic prepared by the present invention has a bending strength which can be up to 82.4-84 MPa, a tensile strength of up to 65.7-66.6 MPa, a notched impact strength of up to 26.3-27 J/m, a melt index of 12.6-15, and an oxygen index of 26.2-27.5%, and thus has excellent mechanical properties and good flame retardancy.

Claims

1. A flame-retardant engineering plastic, comprising a halogen-free flame retardant as a raw material component; the halogen-free flame retardant has a molecular structure as shown by Formula I: ##STR00021## in Formula I, R.sub.1 and R.sub.2 are independently any inert nucleophilic group satisfying the chemical environment thereof; R.sub.3 and R.sub.4 are any organic group satisfying the chemical environment thereof; X.sub.1 and X.sub.2 are independently any one of O—Ar—O—, —S—R.sub.5—S—, —NH—R.sub.6—NH—, —NH—R.sub.7—O—, ##STR00022## —S—R.sub.11NH—, —O—R.sub.12COO— or —S—R.sub.13COO—; R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 are independently any organic group satisfying the chemical environment thereof; Y.sub.1 and Y.sub.2 are independently any nucleophilic group satisfying the chemical environment thereof; M is any one of cyclotriphosphazene groups M.sub.1, a cyclic ring consisting of four or more phosphazene groups M.sub.2, or non-cyclic polyphosphazene groups M.sub.3, or a combination of at least two of them; each m and n is an integer greater than or equal to zero; each a, b, c and d is an integer greater than or equal to zero, and c and d are not zero simultaneously, and a+b+c+d+2 equals to two times of the number of phosphorus atoms in the M group.

2. The engineering plastic of claim 1, characterized in that R.sub.1 and R.sub.2 are independently any one of substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylalkoxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted carboxylate group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, or substituted or unsubstituted phosphonate group; the substituents of alkoxy, cycloalkoxy, aryloxy, arylalkoxy, heteroarylalkoxy, alkylthio group, arylthio group, carboxylate group, carbonate group, sulfonate group or phosphonate group are any one of straight-chain or branched alkyl, alkoxy, cycloalkoxy, aryl, aryloxy, arylalkoxy, heteroaryl, alkylthio group, arylthio group, carboxylate group, carbonate group, sulfonate group or phosphonate group, or a combination of at least two of them; the substituents do not contain reactive capping groups.

3. The engineering plastic of claim 1, characterized in that R.sub.3 and R.sub.4 are independently any one of substituted or unsubstituted straight-chain or branched alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted arylenealkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkyleneheteroarylene, or substituted or unsubstituted heteroarylenealkylene.

4. The engineering plastic of claim 1, characterized in that R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.11, R.sub.12 and R.sub.13 are independently any one of substituted or unsubstituted straight-chain or branched alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted arylenealkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkyleneheteroarylene, or substituted or unsubstituted heteroarylenealkylene.

5. The engineering plastic of claim 1, characterized in that R.sub.9 and R.sub.10 are independently any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, substituted or unsubstituted arylalkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkoxyheteroaryl, substituted or unsubstituted heteroaryloxyalkyl, substituted or unsubstituted alkylheteroaryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted alkylheteroaryl, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted carboxylate group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, or substituted or unsubstituted phosphonate group.

6. The engineering plastic of claim 1, characterized in that Y.sub.1 and Y.sub.2 are independent any one of substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylalkoxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted carboxylate group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, or substituted or unsubstituted phosphonate group.

7. The engineering plastic of claim 1, characterized in that the structure of M.sub.1 is: ##STR00023## the structure of M.sub.2 is: ##STR00024## wherein, x is greater than or equal to 4; the structure of M.sub.3 is: ##STR00025## wherein, y is greater than or equal to 3;

8. The engineering plastic of claim 1, characterized in that M contains at least 50 wt % of M.sub.1, at most 30 wt % of M.sub.2, and at most 45 wt % of M.sub.3.

9. The engineering plastic of claim 1, characterized in that the halogen-free flame retardant is one of the compounds having the following structures, or a combination of at least two of them: ##STR00026## wherein M is a cyclotriphosphazene group.

10. The engineering plastic of claim 1, characterized in that the raw materials of the engineering plastic comprise the following components in parts by mass: 40-60 parts of PC, 20-40 parts of epoxy resin, 10-20 parts of ABS and 5-15 parts of the halogen-free flame retardant of any one of claims 1-3.

11. The engineering plastic of claim 1, characterized in that the epoxy resin is one of liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid bisphenol A type epoxy resin, solid bisphenol F type epoxy resin, bisphenol S type epoxy resin, cyclopentadiene type epoxy resin, or biphenyl type epoxy resin, or a combination of at least two of them.

12. The engineering plastic of claim 1, characterized in that the raw materials of the engineering plastic further contain 0.5-3 parts by mass of additive and 5-25 parts by mass of reinforcing filler.

13. The engineering plastic of claim 1, characterized in that the additive comprises 0.5-1 parts of lubricant, 0.2-0.8 parts of antioxidant, 0.3-0.7 parts of compatibilizer.

14. The engineering plastic of claim 13, characterized in that the lubricant is a TAF lubricant.

15. The engineering plastic of claim 13, characterized in that the antioxidant is n-octadecyl-β-(4-hydroxy-3,5-di-tert-butyl-phenyl)-propionate and organic phosphite powder.

16. The engineering plastic of claim 1, characterized in that the compatibilizer is polysiloxane-acrylate compatibilizer.

17. The engineering plastic of claim 12, characterized in that the reinforcing filler is one of glass fibers, carbon fibers, metal fibers, whiskers, glass sheets and mineral fillers, or a combination of at least two of them.

18. A method for preparing the engineering plastic of claim 1, characterized in that it comprises mixing raw materials comprising the halogen-free flame retardant of claim 1, and subjecting the mixed raw materials to extrusion granulation.

19. The method of claim 18, characterized in that the extrusion granulation is performed by a screw extruder having the following temperatures: 200±0.5° C. in a first zone, 220±0.5° C. in a second zone, 220±0.5° C. in a third zone, 220±0.5° C. in a fourth zone, 240±0.5° C. in a fifth zone, 270±0.5° C. in a sixth zone, 270±0.5° C. in a seventh zone, 270±0.5° C. in an eighth zone, 250±0.5° C. in a ninth zone, 250±0.5° C. in a tenth zone, 280±0.5° C. in an eleventh zone, 280±0.5° C. in a twelfth zone.

Description

EMBODIMENTS

[0089] The technical solutions of the present invention are further explained by combining with the following examples.

[0090] In the following examples, the used raw material of phosphonitrilic chloride (for example hexachlorocyclotriphosphazene) can be obtained by the synthetic methods described in the present invention or known in the art. The other raw materials can be obtained through commercial purchase.

Example 1

[0091] In this example, the halogen-free flame retardant has the following structure:

##STR00014##

[0092] 1 mol of hexachlorocyclotriphosphazene, 250 ml of acetone, 3 mol of bisphenol A and 3 mol of sodium methanethiolate were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60° C. 620 g of 20% sodium hydroxide solution was dripped into the reactor within 60 min, and then the mixture was held at 60° C., stirred and reacted for 15 hours. After reaction, the water in the system was removed by physical methods; the insoluble matters in the system were removed by filtration; and the solvent in the system was distilled off to obtain the above flame-retardant compound.

[0093] The obtained flame-retardant compound was characterized by nuclear magnetic resonance hydrogen spectrum, and the results are as follows:

[0094] .sup.1H NMR (CDCl.sub.3, 500 MHz): □ 6.6-7.0 (m, 24H, hydrogen on benzene ring), 5.0 (s, 3H, hydrogen in phenolic hydroxyl), 2.0 (m, 9H, SCH.sub.3) 1.6 (m, 18H, hydrogen in methyl on bisphenol A group).

[0095] Characteristic peak positions in infrared spectroscopy: characteristic absorption peak of P═N bond in the skeleton of phosphazene, 1217 cm.sup.−1; P—N in the skeleton of phosphazene, 874 cm.sup.−1; absorption peak of methyl ether, 2995 cm.sup.−1; absorption peak of P—O—C bond, 1035 cm.sup.−1; skeleton vibration absorption peaks of benzene ring in bisphenol A group, 1611 cm.sup.−1, 1509 cm.sup.−1, 1446 cm.sup.−1; absorption peaks of phenolic hydroxyl, 3610 cm.sup.−1, 1260 cm.sup.−1.

[0096] 5 parts by mass of flame retardant, 40 parts by mass of PC, 40 parts by mass of epoxy resin, 20 parts by mass of ABS, 0.5 parts by mass of lubricant, 0.2 parts by mass of antioxidant, 0.3 parts by mass of compatibilizer and 5 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic: 199.5° C. in a first zone, 219.5° C. in a second zone, 219.5° C. in a third zone, 219.5° C. in a fourth zone, 239.5° C. in a fifth zone, 269.5° C. in a sixth zone, 269.5° C. in a seventh zone, 269.5° C. in an eighth zone, 249.5° C. in a ninth zone, 249.5° C. in a tenth zone, 279.5° C. in an eleventh zone, 279.5° C. in a twelfth zone.

Example 2

[0097] In this example, the halogen-free flame retardant has the following structure:

##STR00015##

[0098] 1 mol of hexachlorocyclotriphosphazene, 250 ml of acetone and 6 mol of ethanedithiol were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60° C. 620 g of 20% sodium hydroxide solution was dripped into the reactor within 60 min, and then the mixture was held at 60° C., stirred and reacted for 15 hours. After reaction, the water in the system was removed by physical methods; the insoluble matters in the system were removed by filtration; and the solvent in the system was distilled off to obtain the above flame-retardant compound.

[0099] The obtained flame-retardant compound was characterized by nuclear magnetic resonance hydrogen spectrum, and the results are as follows:

[0100] .sup.1H NMR (CDCl.sub.3, 500 MHz): □δ 2.8 (m, 24H, HS—CH.sub.2CH.sub.2S—), 1.5 (s, 6H, HS—CH.sub.2CH.sub.2S—).

[0101] Characteristic peak positions in infrared spectroscopy: characteristic absorption peak of P═N bond in the skeleton of phosphazene, 1217 cm.sup.−1; P—N in the skeleton of phosphazene, 874 cm.sup.−1; absorption peak of methyl ether, 2995 cm.sup.−1; absorption peak of P—O—C bond, 1035 cm.sup.−1; absorption peak of CH.sub.2—S, 2980 cm.sup.−1; absorption peak of —SH, 2560 cm.sup.−1.

[0102] 15 parts by mass of flame retardant, 60 parts by mass of PC, 20 parts by mass of epoxy resin, 20 parts by mass of ABS, 1 parts by mass of lubricant, 0.8 parts by mass of antioxidant, 0.7 parts by mass of compatibilizer and 25 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic: 205.5° C. in a first zone, 220.5° C. in a second zone, 220.5° C. in a third zone, 220.5° C. in a fourth zone, 240.5° C. in a fifth zone, 270.5° C. in a sixth zone, 270.5° C. in a seventh zone, 270.5° C. in an eighth zone, 250.5° C. in a ninth zone, 250.5° C. in a tenth zone, 280.5° C. in an eleventh zone, 280.5° C. in a twelfth zone.

Example 3

[0103] In this example, the halogen-free flame retardant has the following structure:

##STR00016##

[0104] 1 mol of hexachlorocyclotriphosphazene, 250 ml of acetone, 3 mol of thiophenol, 2 mol of sodium methoxide, and lmol of ethylene glycol were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60° C. 620 g of 20% sodium hydroxide solution was dripped into the reactor within 60 min, and then the mixture was held at 60° C., stirred and reacted for 15 hours. Then, 1 mol of hexachlorocyclotriphosphazene was added, and the reaction was continued for 2 hours. Then, 2 mol of hydroquinone and 3 mol of sodium methoxide were added, and the reaction was continued for 6 hours. After reaction, the water in the system was removed by physical methods; the insoluble matters in the system were removed by filtration; and the solvent in the system was distilled off to obtain the above flame-retardant compound.

[0105] The obtained flame-retardant compound was characterized by nuclear magnetic resonance hydrogen spectrum, and the results are as follows:

[0106] .sup.1H NMR (CDCl.sub.3, 500 MHz): □δ 7.0-7.2 (m, 15H, hydrogen on benzene ring in

##STR00017##

group), 6.6 (m, 8H, hydrogen on benzene ring in

##STR00018##

group),

##STR00019##

[0107] 5.0 (m, 2H, hydrogen on hydroxyl in group), 3.7 (d, 4H, O—CH.sub.2CH.sub.2O—), 3.4 (t, 15H, O—CH.sub.3).

[0108] Characteristic peak positions in infrared spectroscopy: characteristic absorption peak of P═N bond in the skeleton of phosphazene, 1217 cm.sup.−1; P—N in the skeleton of phosphazene, 874 cm.sup.−1; absorption peak of methyl ether, 2995 cm.sup.−1; absorption peak of P—O—C bond, 1035 cm.sup.−1; absorption peak of CH.sub.2—O, 2983 cm.sup.−1; absorption peaks of phenolic hydroxy, 3610 cm.sup.−1, 1260 cm.sup.−1.

[0109] 10 parts by mass of flame retardant, 50 parts by mass of PC, 30 parts by mass of epoxy resin, 15 parts by mass of ABS, 0.75 parts by mass of lubricant, 0.5 parts by mass of antioxidant, 0.5 parts by mass of compatibilizer and 15 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic: 200° C. in a first zone, 220.5° C. in a second zone, 220° C. in a third zone, 220° C. in a fourth zone, 240° C. in a fifth zone, 270° C. in a sixth zone, 270° C. in a seventh zone, 270° C. in an eighth zone, 250° C. in a ninth zone, 250° C. in a tenth zone, 280° C. in an eleventh zone, 280° C. in a twelfth zone.

Example 4

[0110] In this example, the halogen-free flame retardant has the following structure:

##STR00020##

[0111] 1 mol of hexachlorocyclotriphosphazene, 250 ml of acetone, 5 mol of ethanedithiol, and 1 mol of hydroquinone were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60° C. 620 g of 20% sodium hydroxide solution was dripped into the reactor within 60 min, and then the mixture was held at 60° C., stirred and reacted for 15 hours. Then, 1 mol of hexachlorocyclotriphosphazene was added, and the reaction was continued for 5 hours. Then, 1 mol of bisphenol A and 4 mol of sodium methoxide were added, and the reaction was continued for 10 hours. After reaction, the water in the system was removed by physical methods; the insoluble matters in the system were removed by filtration; and the solvent in the system was distilled off to obtain the above flame-retardant compound.

[0112] The obtained flame-retardant compound was characterized by nuclear magnetic resonance hydrogen spectrum, and the results are as follows:

[0113] .sup.1H NMR (CDCl.sub.3, 500 MHz): □δ 6.5-7.0 (m, 44H, hydrogen on benzene ring), 5.0 (s, 5H, hydrogen in phenolic hydroxyl), 2.8 (m, 20H, HS—CH.sub.2CH.sub.2S—), 1.7 (s, 30H, hydrogen in methyl), 1.5 (s, 5H, hydrogen in methyl).

[0114] Characteristic peak positions in infrared spectroscopy: characteristic absorption peak of P═N bond in the skeleton of phosphazene, 1217 cm.sup.−1; P—N in the skeleton of phosphazene, 874 cm.sup.−1; absorption peak of methyl ether, 2995 cm.sup.−1; absorption peak of P—O—C bond, 1035 cm.sup.−1; absorption peak of CH.sub.2—O, 2983 cm.sup.−1; skeleton vibration absorption peaks of benzene ring in bisphenol A group, 1611 cm.sup.−1, 1509 cm.sup.−1, 1446 cm.sup.−1; absorption peaks of phenolic hydroxyl, 3610 cm.sup.−1, 1260 cm.sup.−1.

[0115] 8 parts by mass of flame retardant, 60 parts by mass of PC, 20 parts by mass of epoxy resin, 20 parts by mass of ABS, 0.7 parts by mass of lubricant, 0.5 parts by mass of antioxidant, 0.6 parts by mass of compatibilizer and 15 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic:

[0116] 199.5° C. in a first zone, 219.5° C. in a second zone, 220.5° C. in a third zone, 220.5° C. in a fourth zone, 239.5° C. in a fifth zone, 270.5° C. in a sixth zone, 270.5° C. in a seventh zone, 270.5° C. in an eighth zone, 250° C. in a ninth zone, 250.5° C. in a tenth zone, 280.5° C. in an eleventh zone, 280.5° C. in a twelfth zone.

Comparative Example 1

[0117] In this comparative example, an engineering plastic was prepared using a commercially available hexaphenoxycyclotriphosphazene as a flame retardant and in the same manner as that in Example 1. That is, 5 parts by mass of flame retardant, 40 parts by mass of PC, 40 parts by mass of epoxy resin, 20 parts by mass of ABS, 0.5 parts by mass of lubricant, 0.2 parts by mass of antioxidant, 0.3 parts by mass of compatibilizer and 5 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic: 199.5° C. in a first zone, 219.5° C. in a second zone, 219.5° C. in a third zone, 219.5° C. in a fourth zone, 239.5° C. in a fifth zone, 269.5° C. in a sixth zone, 269.5° C. in a seventh zone, 269.5° C. in an eighth zone, 249.5° C. in a ninth zone, 249.5° C. in a tenth zone, 279.5° C. in an eleventh zone, 279.5° C. in a twelfth zone.

Comparative Example 2

[0118] In this comparative example, commercially available aluminum hydroxide is used as a flame retardant. 10 parts by mass of flame retardant, 50 parts by mass of PC, 30 parts by mass of epoxy resin, 15 parts by mass of ABS, 0.75 parts by mass of lubricant, 0.5 parts by mass of antioxidant, 0.5 parts by mass of compatibilizer and 15 parts by mass of glass fiber were mixed sufficiently in a mixing machine. Then, the mixture was extruded and granulated using a screw extruder to obtain a flame-retardant engineering plastic: 200° C. in a first zone, 220.5° C. in a second zone, 220° C. in a third zone, 220° C. in a fourth zone, 240° C. in a fifth zone, 270° C. in a sixth zone, 270° C. in a seventh zone, 270° C. in an eighth zone, 250° C. in a ninth zone, 250° C. in a tenth zone, 280° C. in an eleventh zone, 280° C. in a twelfth zone.

[0119] The cable products of all the above-mentioned examples and comparative examples were tested and the results are shown in Table-1 (the specific test methods are not described considering that they are well-known by those skilled in the art).

TABLE-US-00001 TABLE 1 Com- Com- parative parative Exam- Exam- Exam- Exam- Exam- Test Items Example 1 ple 2 ple 3 ple 4 ple 1 ple 2 Bending 82.6 82.4 84.0 83.6 81 80 strength (MPa) Tensile 65.9 65.7 66.2 65.9 62 63 strength (MPa) Notched 26.6 26.3 27 26.8 21.1 20.8 impact strength (J/m) Melt index 13.2 12.6 15 14 15.7 15.6 (280° C., 2.16 KG) Oxygen 26.2 26.5 27.5 26.8 20 21 index (%, GB/T 2406-2009)

[0120] The test data in the above table show that the engineering plastics of the present invention have bending strength, tensile strength and notched impact strength better than those of the comparative examples, indicating that the addition of the flame retardant material of the present invention can improve mechanical properties. In particular, the flame retardancy of the products of these examples is more outstanding than those of the comparative examples, indicating that the engineering plastics of the present invention have good flame retardancy.

[0121] The applicant states that: the present invention illustrates the engineering plastics of the present invention and preparation methods thereof by the above examples, but the present invention is not limited to the above examples, that is to say, it does not mean that the present invention must be conducted relying on the above examples. Those skilled in the art should understand that any modification to the present invention, any equivalent replacement of each raw material of the products of the present invention and the addition of auxiliary ingredients, the selection of specific embodiment and the like all fall into the protection scope and the disclosure scope of the present invention.