CN118459965B - Elastomer toughened modified polycarbonate and preparation method thereof - Google Patents
Elastomer toughened modified polycarbonate and preparation method thereof Download PDFInfo
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- CN118459965B CN118459965B CN202410921757.8A CN202410921757A CN118459965B CN 118459965 B CN118459965 B CN 118459965B CN 202410921757 A CN202410921757 A CN 202410921757A CN 118459965 B CN118459965 B CN 118459965B
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- polycarbonate
- carbonate
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- polyurethane elastomer
- bisphenol
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 81
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 80
- 229920001971 elastomer Polymers 0.000 title claims abstract description 25
- 239000000806 elastomer Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 48
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001746 injection moulding Methods 0.000 claims description 28
- 239000004970 Chain extender Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- IUEZJNWERGPZHG-UHFFFAOYSA-N C(O)(O)=O.BrC1=CC=CC=C1 Chemical compound C(O)(O)=O.BrC1=CC=CC=C1 IUEZJNWERGPZHG-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims 3
- 238000000034 method Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000001125 extrusion Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000012745 toughening agent Substances 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an elastomer toughened and modified polycarbonate and a preparation method thereof, wherein the elastomer toughened and modified polycarbonate comprises the following raw materials: 65-90 parts by weight of polycarbonate, 10-35 parts by weight of carbonate-based polyurethane elastomer and 0.2-0.5 part by weight of antioxidant; according to the invention, the polycarbonate is blended and modified by using the carbonate-based polyurethane elastomer as the toughening agent, and the polyurethane elastomer contains polyether flexible soft segments and has very high mechanical properties such as toughness, elasticity and the like; meanwhile, the hard segment containing the bisphenol A carbonate structural unit has strong similar compatibility with the carbonate structural unit in the polycarbonate, so that the compatibility between the polyurethane elastomer and the polycarbonate matrix is obviously improved, and the two form an alloy-like phase, so that the polyurethane elastomer has good toughening effect, and the performances of elongation at break, impact strength, bending strength, heat resistance and the like of the polycarbonate are improved.
Description
Technical Field
The invention relates to the technical field of polycarbonate, in particular to elastomer toughened modified polycarbonate and a preparation method thereof.
Background
The polycarbonate PC has excellent flame retardance, good wear resistance and high mechanical property, and is widely applied to the industries of glass assembly industry, automobile industry, electronic and electric appliances and the like. With the rapid development of industry, the traditional polycarbonate cannot meet the requirements of industrial manufacture, and higher requirements are also put on the toughness, strength, heat resistance and other properties of the polycarbonate. Toughening modification of polycarbonate by using rubber elastomers, plastics, nanomaterials and the like is a research hotspot.
The polyurethane plastic, elastomer and other materials have excellent elasticity, toughness and strength, and the preparation method is simple, the cost is low, and the application is very wide. Chinese patent CN111205616B discloses a halogen-free flame-retardant polycarbonate alloy with cold and heat resistance alternation and a preparation method thereof, wherein polycarbonate, modified polyurethane and polysiloxane-polycarbonate copolymer are used as raw materials, silicon-containing core-shell structure acrylic ester polymer is used as a toughening agent, and the obtained polycarbonate alloy has good cold resistance, heat resistance, flame retardance and other properties. However, the raw materials of the patent are complex, the raw materials such as polysiloxane-polycarbonate copolymer, silicon-containing core-shell structure acrylic acid ester polymer and the like are required to be added, and the toughening effect on the polycarbonate material is poor.
Disclosure of Invention
(One) solving the technical problems
The invention solves the problems of poor toughness, poor heat resistance and the like of polycarbonate.
(II) technical scheme
An elastomer toughened and modified polycarbonate comprises the following raw materials: 65-90 parts of polycarbonate, 10-35 parts of carbonate-based polyurethane elastomer and 0.2-0.5 part of antioxidant.
The preparation method of the carbonate-based polyurethane elastomer comprises the following steps:
Adding polyether polyol into a flask, vacuum dehydrating, adding isophorone diisocyanate, heating to 60-70 ℃, reacting for 3-4 hours, adding a naphthyl carbonate chain extender and dibutyl tin dilaurate, rapidly stirring and uniformly mixing for 40-50s, pouring into a preheated mold, and curing after reaching a gel point to obtain the carbonate-based polyurethane elastomer.
The structural formula of the naphthyl carbonate chain extender is as follows:
。
Further, the mol ratio of the polyether polyol to the isophorone diisocyanate to the naphthyl carbonate chain extender is 1 (2.5-2.8): 1.1-1.3); the polyether polyol comprises polyethylene glycol and/or polypropylene glycol.
Further, the curing treatment is carried out for 12-24 hours at 110-120 ℃ and then for 5-7 days at 20-30 ℃.
Further, the preparation method of the naphthyl carbonate chain extender comprises the following steps:
(1) Placing the flask in ice bath, adding dichloromethane, bisphenol A, pyridine and phenyl p-bromochloroformate, stirring at 15-25deg.C for 4-10 hr, filtering, rotary evaporating filtrate, and separating with chromatographic column to obtain bisphenol A carbonate bromobenzene monomer.
(2) Adding N, N-dimethylformamide, bisphenol A carbonate bromobenzene monomer, 6-hydroxynaphthalene-2-boric acid, (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, potassium carbonate and deionized water into a flask, stirring and reacting for 12-18h at 110-130 ℃, adding ethyl acetate and deionized water, uniformly mixing, standing and layering, separating out a water phase, organically drying the ethyl acetate for removing water, performing rotary evaporation, and performing chromatographic column separation to obtain the naphthyl carbonate chain extender.
Further, the mol ratio of bisphenol A, pyridine and phenyl bromochloroformate in (1) is 1 (2-2.2) to (2-2.2).
Further, the mole ratio of bisphenol A carbonate bromobenzene monomer, 6-hydroxynaphthalene-2-boric acid and (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride and potassium carbonate in (2) is 1 (2.3-2.6): 0.044-0.058): 3.4-4.2.
Further, the preparation method of the elastomer toughening modified polycarbonate comprises the steps of placing the polycarbonate, the carbonate-based polyurethane elastomer and the antioxidant into a mixer for uniform mixing, extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210-260 ℃, and finally, injecting in an injection molding machine, wherein the injection pressure is 80-90MPa, and the temperature is 270-280 ℃, so as to obtain the elastomer toughening modified polycarbonate.
(III) beneficial technical effects: bisphenol A is sequentially reacted with phenyl bromochloroformate and 6-hydroxynaphthalene-2-boric acid to obtain a novel naphthyl carbonate chain extender; and then carrying out polymerization reaction with polyether polyol and isophorone diisocyanate to obtain the carbonate-based polyurethane elastomer.
According to the invention, the polycarbonate is blended and modified by using the carbonate-based polyurethane elastomer as the toughening agent, and the polyurethane elastomer contains polyether flexible soft segments and has very high mechanical properties such as toughness, elasticity and the like; meanwhile, the hard segment containing bisphenol A carbonate structural units has strong similar compatibility with carbonate structural units in polycarbonate, so that the compatibility between the polyurethane elastomer and a polycarbonate matrix is remarkably improved, and the two components form an alloy-like phase, so that the polyurethane elastomer has better toughening effect, the elongation at break of the polycarbonate reaches 94.5-139.4%, the impact strength reaches 68.5-95.1kJ/m 2, and the bending strength reaches 88.3-107.0MPa.
The hard segment of the carbonate-based polyurethane elastomer contains naphthalene rings and a plurality of benzene rings, has strong heat resistance, has little influence on the heat resistance of polycarbonate, and can improve the thermal decomposition temperature of a polycarbonate material when the addition amount is proper, so that the polycarbonate shows higher heat resistance.
Drawings
FIG. 1 is a reaction scheme for the preparation of naphthalene based carbonate chain extenders.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
The polycarbonate in the embodiment of the invention is bisphenol A type polycarbonate.
Example 1:
(1) Placing the flask in an ice bath, adding 80mL of dichloromethane, 15 mmol bisphenol A, 30 mmol pyridine and 33mmol of phenyl p-bromochloroformate, stirring at 15 ℃ for reaction for 6 hours, filtering, rotationally evaporating filtrate, separating by a chromatographic column, and obtaining bisphenol A carbonate bromobenzene monomer by eluent of n-hexane and ethyl acetate solution in a volume ratio of 5:1; yield 8.12g.
(2) 60MLN, N-dimethylformamide, 10mmol bisphenol A carbonic ester bromobenzene monomer, 26 mmol 6-hydroxynaphthalene-2-boric acid, 0.44 mmol (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, 34 mmol potassium carbonate and 20mL deionized water are added into a flask, stirred and reacted for 18h at 110 ℃, ethyl acetate and deionized water are added, the mixture is stirred and stirred for standing and layering, water phase is separated, ethyl acetate organic phase is subjected to dry dehydration, rotary evaporation is carried out, chromatographic column separation is carried out, and eluent is n-hexane and ethyl acetate solution with the volume ratio of 3:1, so that the naphthyl carbonic ester chain extender is obtained. The yield was 4.07g.
(3) 20Mmol of polyethylene glycol 1000 is added into a flask, vacuum dehydration is carried out, 50mmol of isophorone diisocyanate is then added, heating is carried out to 60 ℃, reaction is carried out for 4 hours, 22mmol of naphthyl carbonate chain extender and 0.12g of dibutyltin dilaurate are then added, rapid stirring and uniform mixing are carried out for 40 seconds, then the mixture is poured into a preheated mould (the temperature is 110 ℃), after the gel point is reached, the mixture is cured for 12 hours at 120 ℃, and then cured for 7 days at 25 ℃, thus obtaining the carbonate-based polyurethane elastomer.
(4) Placing 900g of polycarbonate, 100g of carbonate-based polyurethane elastomer and 2.8g of antioxidant 1010 into a mixer, uniformly mixing, and then extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 280 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Example 2:
(1) Placing the flask in an ice bath, adding 80mL of dichloromethane, 15 mmol bisphenol A, 30mmol of pyridine and 32mmol of p-bromochloroformate, stirring at 25 ℃ for reaction for 4 hours, filtering, rotationally evaporating filtrate, separating by a chromatographic column, and obtaining bisphenol A carbonate bromobenzene monomer by eluent of n-hexane and ethyl acetate solution in a volume ratio of 5:1; yield 8.04g.
(2) 80MLN, N-dimethylformamide, 10mmol bisphenol A carbonic ester bromobenzene monomer, 26 mmol 6-hydroxynaphthalene-2-boric acid, 0.58 mmol (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, 34 mmol potassium carbonate and 30mL deionized water are added into a flask, stirred and reacted for 12h, ethyl acetate and deionized water are added, the mixture is stirred and stirred for standing and layering, water phase is separated, ethyl acetate organic phase is subjected to dry dehydration, rotary evaporation is carried out, chromatographic column separation is carried out, and eluent is n-hexane and ethyl acetate solution with the volume ratio of 3:1, so that the naphthyl carbonic ester chain extender is obtained. Yield 4.62g.
(3) 20Mmol of polyethylene glycol 1000 is added into a flask, vacuum dehydration is carried out, then 56 mmol isophorone diisocyanate is added, heating is carried out to 60 ℃, reaction is carried out for 4 hours, then 24mmol of naphthyl carbonate chain extender and 0.13g of dibutyl tin dilaurate are added, rapid stirring and uniform mixing are carried out for 50 seconds, then the mixture is poured into a preheated mould (the temperature is 110 ℃), after the gel point is reached, the mixture is cured for 24 hours at 110 ℃, and then cured for 7 days at 20 ℃, thus obtaining the carbonate-based polyurethane elastomer.
(4) Mixing 850g of polycarbonate, 150g of carbonate-based polyurethane elastomer and 2g of antioxidant 1010 uniformly in a mixer, and extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 270 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Example 3:
(1) Placing the flask in an ice bath, adding 100mL of dichloromethane, 15 mmol bisphenol A, 33mmol pyridine and 33mmol of p-bromochloroformate, stirring and reacting for 4 hours at 25 ℃, filtering, rotationally evaporating filtrate, separating by a chromatographic column, and obtaining bisphenol A carbonate bromobenzene monomer by eluent of n-hexane and ethyl acetate solution in a volume ratio of 5:1; yield 7.73g.
(2) 70MLN, N-dimethylformamide, 10mmol bisphenol A carbonic ester bromobenzene monomer, 25 mmol 6-hydroxynaphthalene-2-boric acid, 0.48 mmol (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, 34 mmol potassium carbonate and 20mL deionized water are added into a flask, stirred and reacted for 1h at 130 ℃, ethyl acetate and deionized water are added, the mixture is stirred and layered, water phase is separated, ethyl acetate organic phase is subjected to dry dehydration, rotary evaporation and chromatographic column separation, and eluent is n-hexane and ethyl acetate solution with the volume ratio of 3:1, so that the naphthyl carbonic ester chain extender is obtained. Yield 4.21g.
(3) 20Mmol of polypropylene glycol 1000 is added into a flask, vacuum dehydration is carried out, then 50 mmol isophorone diisocyanate is added, heating is carried out to 60 ℃, reaction is carried out for 4 hours, 22mmol of naphthyl carbonate chain extender and 0.11g of dibutyl tin dilaurate are added, rapid stirring and uniform mixing are carried out for 40 seconds, then the mixture is poured into a preheated mould (the temperature is 110 ℃), after the gel point is reached, the mixture is cured for 24 hours at 110 ℃ and then cured for 7 days at 20 ℃ to obtain the carbonate-based polyurethane elastomer.
(4) 780G of polycarbonate, 220g of carbonate-based polyurethane elastomer and 5g of antioxidant 1010 are placed in a mixer to be uniformly mixed, and then extruded and granulated in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 270 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Example 4:
(1) Placing the flask in an ice bath, adding 80mL of dichloromethane, 15 mmol bisphenol A, 30 mmol pyridine and 33mmol of p-bromochloroformate, stirring and reacting for 10 hours at 20 ℃, filtering, rotationally evaporating filtrate, separating by a chromatographic column, and obtaining bisphenol A carbonate bromobenzene monomer by eluent of n-hexane and ethyl acetate solution in a volume ratio of 5:1; yield 7.82g.
(2) 80MLN, N-dimethylformamide, 10mmol bisphenol A carbonic ester bromobenzene monomer, 23 mmol 6-hydroxynaphthalene-2-boric acid, 0.58 mmol (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, 38 mmol potassium carbonate and 25mL deionized water are added into a flask, stirred and reacted for 18h, ethyl acetate and deionized water are added, the mixture is stirred and stirred for standing and layering, water phase is separated, ethyl acetate organic phase is subjected to dry dehydration, rotary evaporation is carried out, chromatographic column separation is carried out, and eluent is n-hexane and ethyl acetate solution with the volume ratio of 3:1, so that the naphthyl carbonic ester chain extender is obtained. Yield 3.87g.
(3) 20Mmol of polyethylene glycol 1000 is added into a flask, vacuum dehydration is carried out, then 56 mmol isophorone diisocyanate is added, heating is carried out to 65 ℃, reaction is carried out for 4 hours, then 26mmol of naphthyl carbonate chain extender and 0.13g of dibutyl tin dilaurate are added, rapid stirring and uniform mixing are carried out for 40 seconds, then the mixture is poured into a preheated mould (the temperature is 110 ℃), after the gel point is reached, the mixture is cured for 24 hours at 110 ℃, and then cured for 5 days at 30 ℃ to obtain the carbonate-based polyurethane elastomer.
(4) Uniformly mixing 720g of polycarbonate, 280g of carbonate-based polyurethane elastomer and 4g of antioxidant 1010 in a mixer, and extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 90MPa, and the temperature is 270 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Example 5:
(1) Placing the flask in an ice bath, adding 100mL of dichloromethane, 15 mmol bisphenol A, 32mmol pyridine and 32mmol of p-bromochloroformate, stirring and reacting for 6 hours at 20 ℃, filtering, rotationally evaporating filtrate, separating by a chromatographic column, and obtaining bisphenol A carbonate bromobenzene monomer by eluent of n-hexane and ethyl acetate solution in a volume ratio of 5:1; yield 8.39g.
(2) 80MLN, N-dimethylformamide, 10mmol bisphenol A carbonic ester bromobenzene monomer, 26 mmol 6-hydroxynaphthalene-2-boric acid, 0.44 mmol (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, 42 mmol potassium carbonate and 30mL deionized water are added into a flask, stirred and reacted for 12h, ethyl acetate and deionized water are added, the mixture is stirred and stirred for standing and layering, water phase is separated, ethyl acetate organic phase is subjected to dry dehydration, rotary evaporation is carried out, chromatographic column separation is carried out, and eluent is n-hexane and ethyl acetate solution with the volume ratio of 3:1, so that the naphthyl carbonic ester chain extender is obtained. The yield was 4.07g.
(3) 20Mmol of polypropylene glycol 1000 is added into a flask, vacuum dehydration is carried out, then 52 mmol isophorone diisocyanate is added, the temperature is raised to 70 ℃, the reaction is carried out for 3 hours, then 24mmol of naphthyl carbonate chain extender and 0.12g of dibutyl tin dilaurate are added, the mixture is rapidly stirred and mixed for 40 seconds, then the mixture is poured into a preheated mould (the temperature is 110 ℃), after reaching the gel point, the mixture is cured for 24 hours at 110 ℃ and then cured for 7 days at 25 ℃ to obtain the carbonate-based polyurethane elastomer.
(4) Putting 650g of polycarbonate, 350g of carbonate-based polyurethane elastomer and 4g of antioxidant 1010 into a mixer, uniformly mixing, and then extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 280 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Comparative example 1
(1) Mixing 900g of polycarbonate and 2.8g of antioxidant 1010 in a mixer, extruding and granulating in a double screw extruder, wherein the temperature of 1-6 areas is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 280 ℃, so that the polycarbonate material is obtained.
Comparative example 2
(1) 20Mmol of polyethylene glycol 1000 is added into a flask, vacuum dehydration is carried out, 50mmol of isophorone diisocyanate is added, heating is carried out to 60 ℃, reaction is carried out for 4 hours, 22mmol of bisphenol A and 0.12g of dibutyltin dilaurate are added, rapid stirring and uniform mixing are carried out for 40 seconds, then the mixture is poured into a preheated mold (the temperature is 110 ℃), after reaching a gel point, curing is carried out for 12 hours at 120 ℃, and curing is carried out for 7 days at 25 ℃, thus obtaining the polyurethane elastomer.
(2) Placing 900g of polycarbonate, 100g of polyurethane elastomer and 2.8g of antioxidant 1010 into a mixer, uniformly mixing, and then extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 region is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 280 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
Comparative example 3
(1) 20Mmol of polycarbonate diol 1000 is added into a flask, vacuum dehydration is carried out, 50mmol of isophorone diisocyanate is added, heating is carried out to 60 ℃, reaction is carried out for 4 hours, 22mmol of bisphenol A and 0.12g of dibutyltin dilaurate are added, rapid stirring and uniform mixing are carried out for 40 seconds, then the mixture is poured into a preheated mold (the temperature is 110 ℃), after the gel point is reached, curing is carried out for 12 hours at 120 ℃, and then curing is carried out for 7 days at 25 ℃, thus obtaining the carbonate-based polyurethane elastomer.
(2) Placing 900g of polycarbonate, 100g of carbonate-based polyurethane elastomer and 2.8g of antioxidant 1010 into a mixer, uniformly mixing, and then extruding and granulating in a double-screw extruder, wherein the temperature of a 1-6 area is 210 ℃, 240 ℃, 250 ℃, 260 ℃ and 255 ℃; finally, injection molding is carried out in an injection molding machine, the injection molding pressure is 80MPa, and the temperature is 280 ℃, so that the elastomer toughened and modified polycarbonate is obtained.
The tensile properties of the polycarbonate are tested according to GB/T1040.1-2018 standard; bending performance is tested according to GB/T9341-2008 standard; impact properties were tested according to GB/T1843-2008 standard.
Table 1 polycarbonate performance test table
| Tensile Strength (MPa) | Elongation at break (%) | Impact Strength (kJ/m 2) | Flexural Strength (MPa) | |
| Example 1 | 50.6 | 94.5 | 68.5 | 88.3 |
| Example 2 | 62.4 | 112.7 | 73.2 | 96.1 |
| Example 3 | 60.3 | 135.0 | 79.7 | 104.5 |
| Example 4 | 54.8 | 139.4 | 95.1 | 107.0 |
| Example 5 | 48.9 | 127.5 | 92.4 | 99.3 |
| Comparative example 1 | 46.2 | 31.9 | 28.5 | 61.6 |
| Comparative example 2 | 44.6 | 58.2 | 43.8 | 68.9 |
| Comparative example 3 | 55.7 | 77.3 | 60.1 | 79.0 |
The thermal properties of the polycarbonate were tested by thermogravimetric analyzer with nitrogen as the test atmosphere at a temperature ranging from room temperature to 800 ℃. T 5% is the temperature at which the mass loss is 5%. T 50% is the temperature at which 50% of the mass is lost.
TABLE 2 thermal decomposition temperature test of polycarbonate
| T5%（℃） | T50%（℃） | |
| Example 1 | 453.5 | 501.2 |
| Example 2 | 458.8 | 505.9 |
| Example 3 | 460.1 | 503.0 |
| Example 4 | 454.3 | 501.6 |
| Example 5 | 452.5 | 498.8 |
| Comparative example 1 | 456.2 | 502.3 |
| Comparative example 2 | 428.0 | 467.4 |
| Comparative example 3 | 439.7 | 478.8 |
As is clear from tables 1 and 2, the polycarbonate of comparative example 1, to which no polyurethane elastomer was added, had a tensile strength of 46.2MPa, an elongation at break of 31.9%, an impact strength of 28.5kJ/m 2 and a flexural strength of 61.6MPa.
The polycarbonate in examples 1-5 is added with a carbonate-based polyurethane elastomer, and the polyurethane elastomer contains polyether flexible soft segments and has very high mechanical properties such as toughness, elasticity and the like; at the same time containing bisphenol A carbonate structural unit) The hard segment of the polyurethane elastomer has strong similar compatibility with carbonate structural units in the polycarbonate, obviously improves the compatibility between the polyurethane elastomer and a polycarbonate matrix, and forms an alloy-like phase, so that the polyurethane elastomer has good toughening effect, the elongation at break of the polycarbonate reaches 94.5-139.4%, the impact strength reaches 68.5-95.1kJ/m 2, and the bending strength reaches 88.3-107.0MPa. The hard segment of the polyurethane elastomer contains naphthalene rings and a plurality of benzene rings, so that the polyurethane elastomer has strong heat resistance and little influence on the heat resistance of polycarbonate, and when the addition amount is proper, the thermal decomposition temperature of the polycarbonate material can be increased, so that the polycarbonate has higher heat resistance.
In comparison with example 1, comparative example 2 is different in that bisphenol a is used as a chain extender in the preparation of the polyurethane elastomer, and the obtained polyurethane elastomer does not contain carbonate structural units, so that the compatibility between the polyurethane elastomer and polycarbonate is poor, the toughening effect is poor, and the tensile property, impact strength, bending strength and the like of the polycarbonate are lower than those of example 1. And the thermal decomposition temperature is low, and the heat resistance is poor.
In the preparation of the polyurethane elastomer in comparative example 3, polycarbonate diol is used as a soft segment, the compatibility between the obtained polyurethane elastomer and polycarbonate is also good, and the tensile strength of the polycarbonate is obviously improved. However, the polyurethane elastomer is polyester polyurethane, does not contain a flexible polyether segment, has elasticity and toughness lower than those of the polyether polyurethane elastomers in the examples 1-5, and has poor toughening effect, and the properties of the polycarbonate such as elongation at break, impact strength and bending strength are lower than those in the example 1. And the thermal decomposition temperature is low, and the heat resistance is poor.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. The elastomer toughened and modified polycarbonate is characterized by comprising the following raw materials: 65-90 parts by weight of polycarbonate, 10-35 parts by weight of carbonate-based polyurethane elastomer and 0.2-0.5 part by weight of antioxidant;
the preparation method of the carbonate-based polyurethane elastomer comprises the following steps:
Adding polyether polyol into a flask, carrying out vacuum dehydration, then adding isophorone diisocyanate, heating to 60-70 ℃, reacting for 3-4 hours, then adding a naphthyl carbonate chain extender and dibutyl tin dilaurate, rapidly stirring and uniformly mixing for 40-50s, then pouring into a preheated mold, and curing after reaching a gel point to obtain a carbonate-based polyurethane elastomer;
the mol ratio of the polyether polyol to the isophorone diisocyanate to the naphthyl carbonate chain extender is 1 (2.5-2.8): 1.1-1.3); polyether polyols include polyethylene glycol and/or polypropylene glycol;
The preparation method of the naphthyl carbonate chain extender comprises the following steps:
(1) Placing the flask in ice bath, adding dichloromethane, bisphenol A, pyridine and p-bromochloroformate, stirring for reaction, filtering, rotationally evaporating filtrate, and separating by a chromatographic column to obtain bisphenol A carbonate bromobenzene monomer;
(2) Adding N, N-dimethylformamide, bisphenol A carbonate bromobenzene monomer, 6-hydroxynaphthalene-2-boric acid, (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride, potassium carbonate and deionized water into a flask, stirring for reaction, adding ethyl acetate and deionized water, uniformly mixing, standing for layering, separating out water phase, organically drying ethyl acetate for water removal, rotary evaporating, and separating by a chromatographic column to obtain a naphthyl carbonate chain extender;
The mol ratio of bisphenol A, pyridine and p-bromochloroformate in the step (1) is 1 (2-2.2) to 2-2.2;
The mol ratio of bisphenol A carbonic ester bromobenzene monomer, 6-hydroxynaphthalene-2-boric acid, (1, 1' -bis (diphenylphosphino) ferrocene) palladium dichloride and potassium carbonate in the (2) is 1 (2.3-2.6): 0.044-0.058): 3.4-4.2.
2. The elastomer toughened modified polycarbonate as claimed in claim 1, wherein said maturation treatment is carried out by first maturation for 12 to 24 hours at 110 to 120 ℃ and then maturation for 5 to 7 days at 20 to 30 ℃.
3. The elastomer toughened modified polycarbonate as described in claim 1, wherein said reaction temperature in (1) is 15 to 25℃and the reaction time is 4 to 10 hours.
4. The elastomer toughened modified polycarbonate as described in claim 1, wherein said reaction temperature in (2) is from 110 to 130℃and the reaction time is from 12 to 18 hours.
5. A method for preparing the elastomer toughened and modified polycarbonate as described in any one of claims 1 to 4, which is characterized in that the method comprises the steps of uniformly mixing polycarbonate, carbonate-based polyurethane elastomer and antioxidant in a mixer, extruding and granulating in a double-screw extruder, and finally performing injection molding in an injection molding machine to obtain the elastomer toughened and modified polycarbonate.
6. The method for producing an elastomer toughened modified polycarbonate as described in claim 5, wherein said twin screw extruder is extrusion pelletized at a 1-6 zone temperature of 210-260 ℃; the injection pressure of the injection molding machine is 80-90MPa, and the temperature is 270-280 ℃.
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