CN114276382A - Novel silane coupling agent containing nitrogen element, alloy material and preparation method - Google Patents
Novel silane coupling agent containing nitrogen element, alloy material and preparation method Download PDFInfo
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- CN114276382A CN114276382A CN202111538611.8A CN202111538611A CN114276382A CN 114276382 A CN114276382 A CN 114276382A CN 202111538611 A CN202111538611 A CN 202111538611A CN 114276382 A CN114276382 A CN 114276382A
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- flame retardant
- alloy material
- coupling agent
- silane coupling
- acrylonitrile
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- 239000000956 alloy Substances 0.000 title claims abstract description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 105
- 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 claims abstract description 91
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 60
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 40
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 38
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000004417 polycarbonate Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 32
- 230000000996 additive effect Effects 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 238000009396 hybridization Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 229920006026 co-polymeric resin Polymers 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- -1 lipid compounds Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 27
- 229920007019 PC/ABS Polymers 0.000 abstract description 20
- 230000009467 reduction Effects 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000007822 coupling agent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 37
- 229920000515 polycarbonate Polymers 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
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- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
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Abstract
The invention discloses a silane coupling agent containing nitrogen elements and an alloy material, wherein the alloy material comprises the following components in parts by weight: acrylonitrile-butadiene-styrene copolymer, polycarbonate resin, flame retardant, silane coupling agent, compatilizer and other auxiliary agents. The invention has the advantages that the nitrogen element is introduced, the flame retardant property of the composite material using the coupling agent is obviously improved, the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin are combined by the silane coupling agent containing the nitrogen element and having the special functional group, the compatibility between the PC resin and the ABS resin is improved, the problem of material property reduction caused by the addition of the flame retardant is solved, the flame retardant property of the alloy material is improved, the addition of the flame retardant is reduced, the production cost is reduced, the addition of a halogen flame retardant is avoided, the damage of waste gas generated in the injection molding process to a mold, equipment and a human body is reduced, and the popularization and the development of the halogen-free flame retardant PC/ABS alloy material are facilitated.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a novel silane coupling agent containing nitrogen elements, an alloy material and a preparation method.
Background
Polycarbonate (PC) is considered to be an excellent engineering plastic because of its combination of excellent heat resistance, impact resistance, gloss, transparency, dimensional stability, and the like. However, they also have disadvantages such as high cost, stress cracking tendency, poor flowability, poor solvent resistance, and notch sensitivity, and the range of applications of PC is severely limited due to these disadvantages. Acrylonitrile-butadiene-styrene (ABS) has the advantages of low cost, good flowability, high toughness, etc., but its mechanical properties and heat resistance are not ideal. Therefore, the PC and the ABS are prepared into the PC/ABS alloy material, so that the performance complementation can be realized, the performance of the material is improved, and the application range of the material is widened. The PC material has good flame retardant capability, the flame retardant grade of the PC material can reach V2 grade, however, the flame retardant property of the alloy material is reduced to some extent due to the poor flame retardant property of the ABS by preparing the PC and the ABS into an alloy. Therefore, the wide application of the material can be better ensured by carrying out flame-retardant modification on the PC/ABS alloy material.
The existing common flame-retardant modification method of the PC/ABS alloy material mainly comprises two methods of intrinsic flame-retardant modification and filling modification. Among them, the filling method is widely used due to advantages such as simple operation, low cost, and easy industrial production. However, the filling flame-retardant modification method still has disadvantages, such as the mechanical properties of the material are greatly reduced due to the addition of the flame retardant, wherein the reduction of the toughness is most obvious; on the other hand, due to the requirement of environmental protection, common halogen-containing flame retardants have been banned by many countries and regions, and are difficult to pass the strict standard requirements.
In order to solve the problems, the invention provides a special additive with a special functional group structure, which effectively improves the compatibility between PC resin and ABS resin and solves the problem of toughness reduction of PC/ABS alloy materials caused by the addition of a flame retardant. Meanwhile, the special additive can play a synergistic flame-retardant effect, so that the using amount of the flame retardant can be reduced, and the preparation cost of the flame-retardant material is reduced. In addition, compared with the method for preparing the flame-retardant PC/ABS alloy material by adding the BDP flame retardant into the liquid which is widely used at present, the method provided by the invention is simpler to operate. After the high-toughness halogen-free flame-retardant PC/ABS alloy material is applied to small household appliance parts, the high-toughness halogen-free flame-retardant PC/ABS alloy material has the characteristics of high stability, high flame retardance and the like. Is expected to be widely popularized and applied.
Disclosure of Invention
Aiming at the problems of reduced toughness and high preparation cost of PC/ABS alloy materials caused by the addition of the flame retardant, the invention provides the novel silane coupling agent containing the nitrogen element, the preparation method and the application thereof, the alloy materials and the preparation method thereof, the compatibility between the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin is effectively improved, the problem of reduced toughness of the PC/ABS alloy materials caused by the addition of the flame retardant is solved, the dosage of the flame retardant is reduced, and the preparation cost of the flame retardant materials is reduced.
In order to achieve the purpose, the invention provides the following technical scheme: a silane coupling agent containing nitrogen element, the molecular structural formula of which is
In the formula, the substituent groups R and R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
On the other hand, the invention also provides the following technical scheme: a preparation method of a silane coupling agent containing nitrogen elements comprises the following steps:
the amino-containing organosilicon compounds and nitrogen-containing organic lipid compounds are subjected to acylation reaction under the catalysis of sulfuric acid at 120-200 ℃ and 2-6MPa for 20-40min to obtain the amino-containing organosilicon compounds.
Preferably, the preparation reaction principle of the silane coupling agent comprises the following reaction formula:
in the formula, the substituent R and the substituent R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
On the other hand, the invention also provides the following technical scheme: the silane coupling agent is used as an intermediate to combine acrylonitrile-butadiene-styrene copolymer and polycarbonate resin to prepare the composite material, and the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin is improved to improve the toughness of the composite material.
Preferably, the silane coupling agent as an intermediate combines an acrylonitrile-butadiene-styrene copolymer and a polycarbonate resin, comprising:
the imino group of the silane coupling agent and the benzene ring structure of the acrylonitrile-butadiene-styrene copolymer are subjected to conjugate hybridization;
lone pair electrons in the silicon atom of the silane coupling agent and the benzene ring structure of the polycarbonate resin are subjected to conjugate hybridization;
the silane coupling agent is used as an intermediate to improve the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin, so that the toughness of the composite material is improved.
On the other hand, the invention also provides the following technical scheme: the alloy material comprises acrylonitrile-butadiene-styrene copolymer and polycarbonate resin, and according to the application of the silane coupling agent containing the nitrogen element in the composite material, the silane coupling agent containing the nitrogen element combines the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin to prepare the high-toughness halogen-free flame-retardant alloy material.
On the other hand, the invention also provides the following technical scheme: an alloy material comprising the following composition of matter:
acrylonitrile-butadiene-styrene copolymer, polycarbonate resin, flame retardant, special additive, compatilizer and other auxiliary agents;
wherein the special additive is the silane coupling agent containing the nitrogen element.
Preferably, the alloy material comprises the following components in parts by mass:
76.3-80 parts of polycarbonate resin;
6.3-11.3 parts of acrylonitrile-butadiene-styrene copolymer;
6-10 parts of a flame retardant;
0-5 parts of special additive;
0-5 parts of a compatilizer;
0.7 part of other auxiliary agents;
wherein the flame retardant is one or more of a phosphorus flame retardant, a nitrogen flame retardant or an organic phosphorus-nitrogen flame retardant;
the compatilizer is compounded by one or more than two of MBS or SAM;
the other auxiliary agents are one or more than two of an antioxidant and an anti-dripping agent.
Preferably, the mass part ratio of the special additive to the compatilizer is (2.5-3): 1.8-2, and further, the most preferable scheme comprises that the mass part ratio of the special additive to the compatilizer is 3: 2.
Preferably, the ratio of the mass parts of the polycarbonate resin and the acrylonitrile-butadiene-styrene copolymer is (8-12.8): 1, and further, the most preferable scheme comprises that the mass part of the polycarbonate resin is 80% of the total mass part of the alloy material.
Preferably, the mass fraction of the flame retardant is 7.5-8.5% of the total mass fraction of the alloy material, and further, the most preferable scheme includes that the mass fraction of the flame retardant is 8% of the total mass fraction of the alloy material.
On the other hand, the invention also provides the following technical scheme: a preparation method for preparing the alloy material comprises the following steps:
adding polycarbonate resin and acrylonitrile-butadiene-styrene copolymer in a horizontal stirring barrel according to parts or proportion, stirring for 2-5 minutes, and feeding into a double-screw extruder from a feed opening after weight loss;
and adding other auxiliary materials into a high-speed mixer, mixing for 2-5 minutes at the rotating speed of 500r/min, adding the mixture from a double-screw extruder through a side feeding weight loss weighing feeding system, granulating and extruding to obtain the high-toughness halogen-free flame-retardant PC/ABS alloy material.
Preferably, the heating temperature of the double-screw extruder is nine sections, the screw rotating speed is 350r/min, the other auxiliary materials are added when the heating temperature of the fifth section of the double-screw extruder is 200-220 ℃, and the heating temperature of the fifth section is lower than that of the adjacent two sections.
On the other hand, the invention also provides the following technical scheme: a household appliance part comprises the alloy material.
Compared with the prior art, the invention has the following beneficial effects:
the silane coupling agent containing nitrogen elements has the advantages that nitrogen elements are introduced, the flame retardant property of the composite material using the silane coupling agent is obviously improved, meanwhile, silicon dioxide generated by the silicon elements of the silane coupling agent under the thermal action can form a composite inorganic layer with resin carbides, the functions of preventing volatile products generated by combustion from escaping outwards, isolating oxygen from contacting with matrix resin and preventing melting and dropping are achieved, and the generated synergistic flame retardant effect enables the flame retardant property of the composite material to be further improved.
The invention provides an alloy material, wherein a silane coupling agent containing nitrogen elements and having special functional groups is used for combining acrylonitrile-butadiene-styrene copolymer and polycarbonate resin to prepare a high-toughness halogen-free flame-retardant PC/ABS alloy material, so that the compatibility between the PC resin and the ABS resin is improved, the problem of material performance reduction caused by the addition of a flame retardant is solved, the flame retardant performance of the alloy material is improved, the addition of the flame retardant is reduced, the production cost is reduced, the addition of a halogen flame retardant is avoided, the damage of waste gas generated in the injection molding process to molds, equipment and human bodies is reduced, and the popularization and development of the halogen-free flame-retardant PC/ABS alloy material are facilitated.
Drawings
In order to more clearly illustrate the technical solution, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a schematic diagram showing the molecular structural formula of the nitrogen-containing silane coupling agent of the present invention.
FIG. 2 is a schematic view showing the reaction principle for preparing a silane coupling agent according to the present invention.
FIG. 3 is an analytical representation of the compositional formula of the materials of the present invention.
Detailed Description
For clear and complete understanding of the technical solutions, the present invention will now be further described with reference to the embodiments and the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
The first embodiment is as follows:
as shown in figure 1, a silane coupling agent containing nitrogen element has a molecular structural formula of
In the formula, the substituent groups R and R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
The silane coupling agent containing nitrogen elements provided by the embodiment introduces nitrogen elements, so that the flame retardant property of the composite material using the silane coupling agent is obviously improved, meanwhile, silicon dioxide generated by the silicon elements of the silane coupling agent under the thermal action can form a composite inorganic layer with the carbide of resin, the effects of preventing volatile products generated by combustion from escaping, isolating oxygen from contacting with matrix resin and preventing melting and dropping are achieved, and the generated synergistic flame retardant effect enables the flame retardant property of the composite material to be further improved.
The embodiment also provides a preparation method for preparing the silane coupling agent containing the nitrogen element, which comprises the following steps:
carrying out acylation reaction on an amino-containing organosilicon compound and a nitrogen-containing organic lipid compound under the catalysis of sulfuric acid at 120-200 ℃ and 2-6MPa for 20-40min to obtain the compound;
as shown in fig. 2, the reaction principle for preparing the silane coupling agent includes the following reaction formula:
in the formula, the substituent R and the substituent R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
The silane coupling agent containing nitrogen elements prepared by the embodiment has special functional groups at two ends, and when the silane coupling agent is applied to preparation of a halogen-free flame-retardant PC/ABS alloy material with high toughness, the flame-retardant grade of V0 can be ensured, and the heat resistance, the fluidity and the mechanical property of the silane coupling agent are obviously improved.
The embodiment also provides an application of the silane coupling agent containing the nitrogen element in the composite material, the silane coupling agent is used as an intermediate to combine the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin to prepare the composite material, the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin is improved to improve the toughness of the composite material, and the problem of material performance reduction caused by the addition of the flame retardant is solved.
Further, as shown in FIG. 3, the imino group 100 of the silane coupling agent and-CH of the acrylonitrile-butadiene-styrene copolymer2Conjugated hybridization is carried out on the benzene ring structure 200 on the-side, and lone pair electrons in the silicon atom 300 of the silane coupling agent are conjugated hybridization with the benzene ring structure 400 of the polycarbonate resin. The silicon dioxide generated by silicon atoms under the action of heat and the carbide of the resin can form a composite inorganic layer, so that the functions of preventing volatile products generated by combustion from escaping, isolating oxygen from contacting with matrix resin and preventing melting and dropping are achieved, and the generated synergistic flame retardant effect enables the flame retardance of the composite material to be further improved. The silane coupling agent is used as an intermediate to improve the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin, so that the toughness of the composite material is improved, the using amount of a flame retardant is reduced, the problem of material physical property reduction caused by the addition of the flame retardant is solved, and the preparation cost of the flame retardant material is reduced.
The second embodiment:
on the basis of the first embodiment, the embodiment provides an alloy material, which comprises an acrylonitrile-butadiene-styrene copolymer and a polycarbonate resin, and according to the application of the nitrogen-containing silane coupling agent in the composite material, the nitrogen-containing silane coupling agent combines the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin to prepare the high-toughness halogen-free flame-retardant PC/ABS alloy material, so that the problem of material performance reduction caused by the addition of a flame retardant is solved, and the popularization and development of the halogen-free flame-retardant PC/ABS alloy material are facilitated.
The third embodiment is as follows:
an alloy material comprises the following components in parts by mass:
76.3-80 parts of polycarbonate resin;
6.3-11.3 parts of acrylonitrile-butadiene-styrene copolymer;
6-10 parts of a flame retardant, wherein the flame retardant is one or more of a phosphorus flame retardant, a nitrogen flame retardant or an organic phosphorus-nitrogen flame retardant;
0-5 parts of a special additive, wherein the special additive is a silane coupling agent containing nitrogen element described in the first embodiment;
0-5 parts of a compatilizer, wherein the compatilizer is compounded by one or more than two of MBS or SAM;
0.7 part of other auxiliary agents, wherein the other auxiliary agents are one or more than two of an antioxidant and an anti-dripping agent;
the embodiment also provides a preparation method for preparing the alloy material, which comprises the following steps:
adding polycarbonate resin and acrylonitrile-butadiene-styrene copolymer in a horizontal stirring barrel according to parts or proportion, stirring for 2-5 minutes, and feeding into a double-screw extruder from a feed opening after weight loss;
and adding other auxiliary materials into a high-speed mixer, mixing for 2-5 minutes at a rotating speed of 500r/min, adding the mixture from a double-screw extruder through a side-feeding weight loss weighing and feeding system, granulating and extruding, wherein the heating temperature of the double-screw extruder is nine sections, the rotating speed of the screw is 350r/min, the heating temperatures of the nine sections are respectively and sequentially configured to be 190 ℃, 200 ℃, 205 ℃, 210 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and 230 ℃, and the other auxiliary materials are added when the heating temperature of the fifth section of the double-screw extruder is 200-220 ℃, so that the high-toughness halogen-free flame-retardant PC/ABS alloy material is finally obtained.
According to the high-toughness halogen-free flame-retardant PC/ABS alloy material prepared by the embodiment, the silane coupling agent containing nitrogen elements and having special functional groups is added, so that the compatibility between the PC resin and the ABS resin is improved, and the problem of material property reduction caused by the addition of the flame retardant is solved.
Further, as shown in fig. 3, in the present embodiment, a carbonyl oxygen 500 at the left end of the compatibilizer contains a pair of lone pair electrons, which can perform conjugate hybridization with a benzene ring structure 600 in the PC resin, and a benzene ring structure 700 at the other end of the compatibilizer can perform conjugate hybridization with a cyano group 800 at the left end of the ABS resin, so that the compatibilizer can be used as an intermediate to combine the ABS resin and the PC resin together, thereby improving the toughness of the composite material. Similarly, the amino 100 on the left side of the nitrogen-containing silane coupling agent can perform conjugate hybridization with the benzene ring structure 200 in the ABS resin, and the lone pair of electrons in the silicon atom 300 on the right side can perform conjugate hybridization with the benzene ring structure 400 in the PC resin, so that the nitrogen-containing silane coupling agent can be used as an intermediate to improve the compatibility between the ABS resin and the PC resin, thereby improving the toughness of the material.
The embodiment improves the physical property of the PC/ABS alloy material by using the silane coupling agent containing the nitrogen element, reduces the influence of the halogen-free flame retardant on the physical property of the material, improves the flame retardant property of the alloy material, reduces the addition of the flame retardant, reduces the production cost, avoids the addition of the halogen flame retardant, and reduces the damage of waste gas generated in the injection molding process to molds, equipment and human bodies.
The embodiment also provides a testing method, corresponding test samples are prepared according to the preparation method of the embodiment by different parts by mass of the material components of the alloy material provided by the embodiment, and the parameter configuration selected by the prepared test samples can also be implemented as another embodiment, which is one or more of the preferred embodiments of the invention, is used for helping to understand the inventive concept of the technical scheme, and does not limit the invention in other forms.
The test sample comprises the following material components in parts by mass:
test sample 1:
80 parts of polycarbonate resin (hereinafter referred to as PC resin), 6.3 parts of acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS resin), 8 parts of halogen-free flame retardant, 3 parts of special additive, 2 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 2:
80 parts of PC resin, 6.3 parts of ABS resin, 8 parts of halogen-free flame retardant, 2 parts of special additive, 3 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 3:
80 parts of PC resin, 6.3 parts of ABS resin, 8 parts of halogen-free flame retardant, 5 parts of special additive, 0 part of compatilizer and 0.7 part of other auxiliary agent.
Test sample 4:
80 parts of PC resin, 6.3 parts of ABS resin, 8 parts of halogen-free flame retardant, 0 part of special additive, 5 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 5:
80 parts of PC resin, 11.3 parts of ABS resin, 8 parts of halogen-free flame retardant, 0 part of special additive, 0 part of compatilizer and 0.7 part of other auxiliary agent.
Test sample 6:
76.3 parts of PC resin, 10 parts of ABS resin, 8 parts of halogen-free flame retardant, 3 parts of special additive, 2 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 7:
80 parts of PC resin, 6.3 parts of ABS resin, 8 parts of halogen-free flame retardant, 0 part of special additive, 3 parts of unmodified additive, 2 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 8:
78 parts of PC resin, 6.3 parts of ABS resin, 10 parts of halogen-free flame retardant, 3 parts of special additive, 2 parts of compatilizer and 0.7 part of other auxiliary agent.
Test sample 9:
80 parts of PC resin, 8.3 parts of ABS resin, 6 parts of halogen-free flame retardant, 3 parts of special additive, 2 parts of compatilizer and 0.7 part of other auxiliary agent.
The test method comprises the steps of injection molding tensile sample strips, bending sample strips, flame-retardant sample strips and impact sample strips in an injection molding machine at the temperature of 190-280 ℃, and performing performance test on the sample strips according to national standard, wherein the test sample strips are kept still for 88h under the environmental conditions of 23 +/-2 ℃ and the humidity of 50 +/-10% before the test, and the parameters of the injection molded sample strips are as follows:
tensile bar size: the length is 150 plus or minus 2mm, the width is 10 plus or minus 0.2mm, and the thickness is 4 plus or minus 0.2 mm;
bending spline size: the length is 80 plus or minus 2mm, the width is 10 plus or minus 0.2mm, and the thickness is 4 plus or minus 0.2 mm;
impact spline size: the length is 80 plus or minus 2mm, the width is 10 plus or minus 0.2mm, and the thickness is 4 plus or minus 0.2 mm;
heat distortion spline size: the length is 80 plus or minus 2mm, the width is 10 plus or minus 0.2mm, and the thickness is 4 plus or minus 0.2 mm;
flame retardant sample size: the length is 125 +/-5 mm, the width is 13 +/-0.5 mm, and the thickness is 1.5 +/-0.1 mm.
And (3) preparing a corresponding test sample strip from the test sample, and testing to obtain the following test results:
from the above table test results it is known that:
according to the test results of the test samples 1-5, under the condition of controlling the mass parts of other substance components to be unchanged, the mass parts of the special additive and the compatilizer are changed, and the tensile strength, the bending strength, the heat distortion temperature and the melt index of the prepared test sample are not obviously changed; from the aspect of notch impact strength, the toughness of the test sample after the synergistic action of the special additive and the compatilizer is higher than the strength of the test sample after the synergistic action of the special additive and the compatilizer is adopted, wherein when the mass part ratio of the special additive to the compatilizer is 3:2, the toughness (taking notch impact as an example) of the prepared alloy material is optimal.
It is known from the test results of the test sample 6 and the test sample 1 that, under the condition of controlling the mass parts of other material components to be unchanged, although the addition proportion of the ABS resin in the alloy material can be increased to improve part of the physical properties of the alloy material, the notch impact strength of the alloy material is reduced because the toughness of the ABS resin is lower than that of the PC resin; in addition, since the heat resistance of the ABS resin is lower than that of the PC resin, which leads to a decrease in the heat distortion temperature of the alloy material, the PC resin is optimally disposed such that 80% of the total mass fraction of the alloy material is satisfied in order to satisfy the heat resistance requirement of the material (with the heat distortion temperature of 100 ℃).
According to the test results of the test sample 7 and the test sample 1, under the condition that the mass parts of other substance components are controlled to be unchanged, after the special additive is replaced by the unmodified additive, the flame retardant performance of the unmodified additive is not good, so that the flame retardant grade of the material only reaches the V1 grade.
According to the test results of the test sample 8, the test sample 9 and the test sample 1, the change of the mass fraction of the flame retardant has obvious influence on the physical properties of the alloy material, and when the flame retardant is excessive (taking 10% as an example), the notch impact strength of the alloy material is reduced in a slope breaking manner, which indicates that the excessive addition of the flame retardant hinders the compatibility of the PC resin and the ABS resin; when the addition of the flame retardant is insufficient (taking 6% as an example), although the physical properties of the alloy material are not obviously reduced compared with the test sample 1, the material cannot reach the flame retardant rating of V0 due to the insufficient content of the flame retardant, so the mass part of the halogen-free flame retardant is optimal when the mass part is 8 parts on the premise of the mixture ratio of the components of the test sample.
The embodiment also provides an alloy material, wherein the mass part ratio of the special additive is 2.5-3: 1.8-2, and further, the most preferable scheme comprises that the mass part ratio of the special additive to the compatilizer is 3: 2.
The embodiment also provides an alloy material, wherein the mass part ratio of the polycarbonate resin to the acrylonitrile-butadiene-styrene copolymer is 8-12.8: 1, and further, the most preferable scheme is that the mass part of the polycarbonate resin is 80% of the total mass part of the alloy material.
The embodiment also provides an alloy material, wherein the mass part of the flame retardant is 7.5-8.5% of the total mass part of the alloy material, and further, the most preferable scheme comprises that the mass part of the flame retardant is 8% of the total mass part of the alloy material.
On the other hand, the embodiment also provides a household appliance part, the household appliance part comprises the alloy material, and the household appliance part with the high-toughness halogen-free flame-retardant PC/ABS alloy material has the characteristics of high stability and high flame retardance.
The above disclosure is intended to be illustrative of one or more of the preferred embodiments of the present invention and is not intended to limit the invention in any way, which is equivalent or conventional to one skilled in the art and which is intended to cover all modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims.
Claims (14)
1. The silane coupling agent containing nitrogen elements is characterized in that the molecular structural formula is
In the formula, the substituent groups R and R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
2. A method for producing the nitrogen element-containing silane coupling agent according to claim 1, comprising:
the amino-containing organosilicon compounds and nitrogen-containing organic lipid compounds are subjected to acylation reaction for 20-40min under the catalysis of sulfuric acid at 120-200 ℃ and 2-6 MPa.
3. A method of manufacturing according to claim 2, wherein: the preparation reaction principle of the silane coupling agent comprises the following reaction formula:
in the formula, the substituent R and the substituent R' are respectively one or more than two of methyl, ethyl, phenyl, alkyl and hydrogen atoms.
4. The application of the silane coupling agent containing the nitrogen element in the composite material is characterized in that: the silane coupling agent is used as an intermediate to combine the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin to prepare the composite material, and the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin is improved to improve the toughness of the composite material.
5. A use according to claim 4, characterized in that: the silane coupling agent as an intermediate for combining an acrylonitrile-butadiene-styrene copolymer with a polycarbonate resin, comprising:
the imino group of the silane coupling agent and the benzene ring structure of the acrylonitrile-butadiene-styrene copolymer are subjected to conjugate hybridization;
lone pair electrons in the silicon atom of the silane coupling agent and the benzene ring structure of the polycarbonate resin are subjected to conjugate hybridization;
the silane coupling agent is used as an intermediate to improve the compatibility of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate resin, so that the toughness of the composite material is improved.
6. An alloy material comprising an acrylonitrile-butadiene-styrene copolymer and a polycarbonate resin, characterized in that: combining the acrylonitrile-butadiene-styrene copolymer and polycarbonate resin using the application of claim 4 or 5 to produce a high toughness halogen free flame retardant alloy material.
7. An alloy material, characterized by comprising the following composition of matter:
acrylonitrile-butadiene-styrene copolymer, polycarbonate resin, flame retardant, special additive, compatilizer and other auxiliary agents;
wherein the special additive is the silane coupling agent containing nitrogen element according to any one of claims 1 to 3.
8. The alloy material as claimed in claim 7, characterized by comprising the following components in parts by mass:
76.3-80 parts of polycarbonate resin;
6.3-11.3 parts of acrylonitrile-butadiene-styrene copolymer;
6-10 parts of a flame retardant;
0-5 parts of special additive;
0-5 parts of a compatilizer;
0.7 part of other auxiliary agents;
wherein the flame retardant is one or more of a phosphorus flame retardant, a nitrogen flame retardant or an organic phosphorus-nitrogen flame retardant;
the compatilizer is compounded by one or more than two of MBS or SAM;
the other auxiliary agents are one or more than two of an antioxidant and an anti-dripping agent.
9. An alloy material according to claim 7, wherein: the mass part ratio of the special additive to the compatilizer is (2.5-3) to (1.8-2).
10. An alloy material according to claim 7, wherein: the mass part ratio of the polycarbonate resin to the acrylonitrile-butadiene-styrene copolymer is (8-12.8) to 1.
11. An alloy material according to claim 7, wherein: the mass portion of the flame retardant is 7.5-8.5% of the total mass portion of the alloy material.
12. A method for preparing an alloy material according to any one of claims 6 to 11, comprising the steps of:
adding polycarbonate resin and acrylonitrile-butadiene-styrene copolymer in a horizontal stirring barrel according to parts or proportion, stirring for 2-5 minutes, and feeding into a double-screw extruder from a feed opening after weight loss;
and adding other auxiliary materials into a high-speed mixer, mixing for 2-5 minutes at the rotating speed of 500r/min, adding the mixture from a double-screw extruder through a side feeding weight loss weighing feeding system, granulating and extruding to obtain the high-toughness halogen-free flame-retardant PC/AB alloy material.
13. The production method according to claim 12, characterized in that: the heating temperature of the double-screw extruder is nine sections, the rotating speed of the screws is 350r/min, other auxiliary materials are added when the heating temperature of the fifth section of the double-screw extruder is 200-220 ℃, and the heating temperature of the fifth section is configured to be lower than that of the adjacent two sections.
14. A component part for a household appliance, comprising: the household appliance component comprises an alloy material according to claims 6-11.
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