CN111171325B - Polycarbonate low-temperature toughening modifier, preparation method and toughening method - Google Patents

Polycarbonate low-temperature toughening modifier, preparation method and toughening method Download PDF

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CN111171325B
CN111171325B CN202010069466.2A CN202010069466A CN111171325B CN 111171325 B CN111171325 B CN 111171325B CN 202010069466 A CN202010069466 A CN 202010069466A CN 111171325 B CN111171325 B CN 111171325B
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CN111171325A (en
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马文中
彭辉
杨海存
李润飞
龚方红
刘春林
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Changzhou University
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    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
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    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention discloses a polycarbonate low-temperature toughening modifier, a preparation method and a toughening method, wherein the preparation method comprises the steps of (1) dissolving hydroxyl-terminated liquid silicone rubber into an organic solvent A, adding a diisocyanate modifier and a catalyst A, reacting at a certain temperature, continuously adding alkynyl alcohol into the solution, reacting again under stirring, and purifying after the reaction is finished to obtain alkynyl-terminated liquid silicone rubber; (2) fully dissolving a certain proportion of alkynyl-terminated liquid silicone rubber and azido ABS in a proper amount of organic solvent B, adding catalyst B, stirring and reacting at 25-60 ℃ for 24-48h, and then purifying to obtain the cross-linked silicone rubber graft ABS copolymer. And the toughening modifier is prepared based on the preparation method and is heated in the PC resin to realize the improvement of the plasticity performance of the PC resin.

Description

Polycarbonate low-temperature toughening modifier, preparation method and toughening method
Technical Field
The invention belongs to the field of polymer modification, and particularly relates to a polycarbonate low-temperature toughening modifier, a preparation method and a toughening method.
Background
Compared with general plastics such as polyolefin and the like, special engineering plastics such as Polycarbonate (PC), polyphenylene oxide (PPO), polyether ether ketone (PEEK) and the like have higher mechanical properties, can stand wider temperature change and harsh environmental conditions, and can be used as structural materials in engineering. However, most of special engineering plastics have a rigid chain structure with aromatic heterocyclic rings, which determines that the melt viscosity is high, the processing temperature is high, products are easy to generate internal stress, a stress cracking phenomenon occurs, and the notch sensitivity is high. Like PC, although the flexibility of ether group in PPO is greatly increased by carbonyl and ester group adjacent to benzene ring, molecular chain of PC still has great rigidity, resulting in higher glass transition temperature. The relative slippage between molecules is difficult, and the melting temperature is also increased, and the melt viscosity is very high. The rigid molecular chain blocks the movement of the macromolecular chain, so that the residual internal application in the product is difficult to eliminate by self, and the stress cracking phenomenon occurs. Although PC has higher impact strength at normal temperature, PC has low impact strength and high notch sensitivity and is easy to generate stress cracking phenomenon at low temperature, and the application of PC is greatly limited by the defects. Therefore, low-temperature toughening modification of PC is urgently needed, so that the impact strength of PC at low temperature is improved, the notch sensitivity is reduced, and the application range of PC is widened.
Elastomer toughening of modified PCs is a common practice, with styrenic elastomers being the more developed and most widely used class of thermoplastic elastomers. The benzene ring in the elastomer has certain compatibility with PC, and the soft segments of butadiene, isoprene and the like have rubber elasticity, so that the stress cracking phenomenon of the elastomer can be effectively improved after the elastomer is blended with PC. The polymer with a core-shell structure is also a modifier commonly used for toughening PC, such as core-shell particles of ABS, MBS, ACR and the like, the outer hard shell can improve the compatilizer of the particles and PC, and the inner rubber core plays a role in improving the notch impact strength of the PC. The ABS toughening PC is a relatively mature method in an earlier research, the SAN section in the ABS has better compatibility with the PC, and the PB section not only can endow the blend with better low-temperature toughness, but also can reduce the melt viscosity and improve the processability. In addition, blending of polyolefin materials with PC is also an effective method for improving the toughness of the polyolefin materials, and can reduce the material cost, but the compatibility of the polyolefin materials and PC is poor, and a proper compatilizer needs to be added. The toughening modifier can show obvious toughening effect only by needing to be in higher content, so that the strength of the material is obviously reduced.
Compared with the C-O bond in the common toughening component, the flexibility of the Si-O bond is higher, so that most organosilicon polymers have extremely low glass transition temperature (below-100 ℃), and the low-temperature toughening modification method is the best choice for PC low-temperature toughening modification. At present, most of research reports on organosilicon toughening PC realize low-temperature toughening by preparing polysiloxane-g-PC block copolymer by a chemical modification method, and few research reports on blending modification of organosilicon macromolecules and PC are related, mainly because common organosilicon polymers such as silicone rubber and PC compatilizer are extremely poor.
Disclosure of Invention
Aiming at the problems, the invention provides a polycarbonate low-temperature toughening modifier, a preparation method and a toughening method.
The technical purpose is achieved, the technical effect is achieved, and the invention is realized through the following technical scheme:
a preparation method of a polycarbonate low-temperature toughening modifier comprises the following steps:
(1) dissolving hydroxyl-terminated liquid silicone rubber in an organic solvent A, adding a diisocyanate modifier and a catalyst A, reacting at a certain temperature, continuously adding alkynyl alcohol into the solution, reacting again under stirring, and purifying after the reaction is finished to obtain alkynyl-terminated liquid silicone rubber;
(2) fully dissolving a certain proportion of alkynyl-terminated liquid silicone rubber and azido ABS in a proper amount of organic solvent B, adding catalyst B, stirring and reacting at 25-60 ℃ for 24-48h, and then purifying to obtain the cross-linked silicone rubber graft ABS copolymer.
As a further improvement of the invention, the molar ratio of the diisocyanate modifier to the hydroxyl-terminated liquid silicone rubber in the step (1) is 2:1-3:1, and the molar ratio of the alkynylalcohol to the diisocyanate modifier is 1:1-2: 1. By the above modification a reasonable number of reactive sites on the backbone are obtained.
As a further improvement of the invention, the catalyst A is selected from dibutyltin dilaurate or stannous octoate, the catalyst B is selected from cuprous chloride or cuprous bromide, the reaction temperature of the reaction between the diisocyanate modifier and the hydroxyl-terminated liquid silicone rubber in the step (1) is 50-100 ℃, and the reaction time is 12-24 h.
As a further improvement of the invention, the diisocyanate modifier is any one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
As a further improvement of the invention, in the step (1), the molecular weight of the hydroxyl-terminated liquid silicone rubber is 10-50 ten thousand. Firstly, the molecular weight of a main chain is selected to avoid that the toughening effect of the finally prepared toughening agent cannot be achieved due to too small molecular weight and too large crosslinking density, or avoid that the mobility of the toughening agent is reduced and the generation of cracks is increased due to too large molecular weight of the toughening agent, so that the prepared toughening agent can finally show good mobility and reaction activity, and the experimental purpose of the invention is achieved.
As a further improvement of the invention, the mass ratio of the alkynyl-terminated liquid silicone rubber to the azide ABS in the step (2) is 2:1-4: 1. Not only ensures the smooth proceeding of the graft polymerization and can obtain a reasonable number of graft chains, but also avoids the residual redundant reaction raw materials and increases the burden of subsequent purification.
As a further improvement of the invention, the method also comprises the step of preparing the azide ABS, and the prepared azide ABS is stored in a dry environment at the temperature of less than 10 ℃ and protected from light.
As a further improvement of the invention, the purification step in the step (2) comprises the following steps:
firstly, precipitating a solid product by using excessive absolute ethyl alcohol;
and then repeatedly washing with EDTA salt solution to remove the catalyst, thus obtaining the cross-linked silicone rubber graft ABS copolymer.
The invention also discloses a polycarbonate low-temperature toughening modifier which is the cross-linking type silicon rubber grafted ABS copolymer prepared on the basis of the preparation method.
The invention also discloses a low-temperature toughening method of polycarbonate, in particular to a method for adding 1-5% by mass of the cross-linked silicone rubber grafted ABS copolymer prepared by the preparation method into the polycarbonate.
The invention has the beneficial effects that:
1. the alkynyl functionalized liquid silicone rubber and the azide ABS resin are respectively prepared by chemical modification, and the graft copolymer of the silicone rubber and the ABS is obtained by click reaction.
2. The toughening modifier prepared by the invention is a cross-linked silicone rubber grafted ABS copolymer, the glass transition temperature is near-130 ℃, and the low-temperature resistance is better; and a cross-linking structure is formed between the liquid silicon rubber and the ABS, the SAN component in the ABS is used for compatibilization, the coordination toughening effect of the silicon rubber and the PB component in the ABS is fully exerted, the low-temperature toughness of the PC can be obviously improved when the using amount is within 5%, and the reduction of the tensile strength can be controlled within 3%.
Drawings
FIG. 1 is a schematic structural diagram of a cross-linked silicone rubber grafted ABS copolymer prepared by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following detailed description of the principles of the invention is provided in connection with the accompanying drawings.
As shown in FIG. 1, the modifier for toughening polycarbonate at low temperature prepared by the invention has a schematic structure, and the toughening modifier is a cross-linked silicone rubber grafted ABS copolymer. Chemical crosslinking is carried out through click reaction between the nitrified ABS side group and the alkynyl liquid silicon rubber end group, and the structure can fully play the compatibilization role of ABS and the low-temperature toughening role of silicon rubber in cooperation with the ABS.
The preparation method of the modifier mainly comprises the following steps:
example 1
(1) Preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 15 ten thousand in a proper amount of toluene, adding a proper amount of modifier toluene diisocyanate and a catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at 60 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in appropriate amount of 1, 2-dichloroethane, adding sufficient liquid bromine and AIBN, sealing, stirring at 70 deg.C for 10 hr, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide. Due to poor stability of the azido ABS, the prepared azido ABS is usually stored in a low-temperature dry environment and protected from light to reduce the reaction activity. In the overall process of preparing the low-temperature toughening modifier, the recently prepared azide ABS is generally used for reaction, so that the grafting rate of the azide ABS with a main chain silicon rubber chain is improved.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 2:1 in a proper amount of N, N dimethylformamide, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using an EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 2
(1) Preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 20 ten thousand in proper amount of dimethylbenzene, adding proper amount of modifier diphenylmethane diisocyanate and catalyst stannous octoate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at the temperature of 50 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of toluene, adding sufficient liquid bromine and AIBN, sealing, stirring at 75 deg.C for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 3:1 in a proper amount of organic solvent, adding a proper amount of cuprous bromide, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove the catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 3
A cross-linking silicone rubber graft ABS copolymer for polycarbonate low-temperature toughening modification and a preparation method thereof mainly comprise the following steps:
(1) preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 25 ten thousand in a proper amount of dimethylbenzene, adding a proper amount of modifier diphenylmethane diisocyanate and catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at 80 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of xylene, adding sufficient liquid bromine and BPO, sealing, stirring at 80 ℃ for reaction for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 4:1 in a proper amount of organic solvent, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 4
A cross-linking silicone rubber graft ABS copolymer for polycarbonate low-temperature toughening modification and a preparation method thereof mainly comprise the following steps:
(1) preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 25 ten thousand in a proper amount of dimethylbenzene, adding a proper amount of modifier diphenylmethane diisocyanate and catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at 80 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of xylene, adding sufficient liquid bromine and BPO, sealing, stirring at 80 ℃ for reaction for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 3:1 in a proper amount of organic solvent, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 5
A cross-linking silicone rubber graft ABS copolymer for polycarbonate low-temperature toughening modification and a preparation method thereof mainly comprise the following steps:
(1) preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 25 ten thousand in a proper amount of dimethylbenzene, adding a proper amount of modifier diphenylmethane diisocyanate and catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at 80 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of xylene, adding sufficient liquid bromine and BPO, sealing, stirring at 80 ℃ for reaction for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 2:1 in a proper amount of organic solvent, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 6
A cross-linking silicone rubber graft ABS copolymer for polycarbonate low-temperature toughening modification and a preparation method thereof mainly comprise the following steps:
(1) preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 10 in a proper amount of dimethylbenzene, adding a proper amount of modifier diphenylmethane diisocyanate and catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10 hours at 80 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of xylene, adding sufficient liquid bromine and BPO, sealing, stirring at 80 ℃ for reaction for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 3:1 in a proper amount of organic solvent, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Example 7
A cross-linking silicone rubber graft ABS copolymer for polycarbonate low-temperature toughening modification and a preparation method thereof mainly comprise the following steps:
(1) preparation of alkynyl terminated linear liquid silicone rubber: dissolving hydroxypropyl terminated liquid silicon rubber with the molecular weight of 50 ten thousand in proper amount of dimethylbenzene, adding proper amount of modifier diphenylmethane diisocyanate and catalyst dibutyltin dilaurate, wherein the molar ratio of the modifier to the liquid silicon rubber is 2:1, and reacting for 10h at 80 ℃. And after the reaction is finished, cooling to room temperature, continuously adding a proper amount of propiolic alcohol into the solution, wherein the molar ratio of the propiolic alcohol to the isocyanate modifier is 2:1, stirring and reacting for 24 hours at the room temperature, after the reaction is finished, using excessive distilled water to react to remove residual isocyanate, separating out a precipitate, and freeze-drying the precipitate to obtain the alkynyl-terminated liquid silicone rubber.
(2) Preparation of azido ABS: dissolving ABS in proper amount of xylene, adding sufficient liquid bromine and BPO, sealing, stirring at 80 ℃ for reaction for 10h, precipitating with petroleum ether, and vacuum drying to obtain brominated ABS; dissolving ABS bromide in a proper amount of tetrahydrofuran, adding sufficient sodium azide and a catalyst tetrabutylammonium azide, refluxing, stirring, reacting for 48 hours, precipitating by using excessive petroleum ether, washing by using distilled water for a plurality of times, then washing by using ethyl ether, and drying in vacuum to obtain the ABS azide.
(3) Preparing a cross-linked silicone rubber grafted ABS copolymer by alkynyl-azide click reaction: fully dissolving alkynyl liquid silicon rubber and azido ABS in a mass ratio of 3:1 in a proper amount of organic solvent, adding a proper amount of cuprous chloride, stirring and reacting at 50 ℃ for 48 hours, precipitating a solid product by using excessive absolute ethyl alcohol, and repeatedly washing by using EDTA salt solution to remove a catalyst to obtain the cross-linked silicon rubber grafted ABS copolymer.
Application performance testing
The low-temperature toughening modified particles prepared in the examples 1-7 are melt blended with PC according to the proportion of 1% -5%, injection molded into standard sample bars, and tested for tensile and impact properties according to GB/T1040-2006 and GB/T1843-2008, wherein the PC is 1225L, and the test results are shown in Table 1. Wherein the strength of a cantilever notched impact test immediately after freezing a sample having a modifier content of 5% with liquid nitrogen was 33 kJ.m-2。
Figure GDA0003146050060000071
Figure GDA0003146050060000081
From the above data it can be seen that:
(1) when 1-5% of the toughening agent prepared by the invention is added into the PC resin, the impact resistance lightness and the elongation at break of the PC resin are obviously improved, which shows that the toughening agent prepared by the invention can well improve the toughness of the PC resin, wherein the toughening effect of the PC resin is most obvious after the toughening agent with the mass fraction of 5% in example 3 is used.
(2) The molecular weight of the hydroxypropyl end capping liquid silicon rubber in the toughening agent prepared by the invention is selected within the range of 10-50 ten thousand, the plasticity of the PC resin is improved to a certain extent, and the effect of the toughening agent prepared by selecting the hydroxypropyl end capping liquid silicon rubber with the mass fraction of about 25 ten thousand is optimal.
(3) When the mass fraction of the alkynyl liquid silicone rubber and the azido ABS is controlled within the range of 2:1-4:1 in the preparation process, the prepared toughening agent has sufficient graft polymerization reaction and can introduce a number of graft chains.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The preparation method of the polycarbonate low-temperature toughening modifier is characterized by comprising the following steps of:
(1) dissolving hydroxyl-terminated liquid silicone rubber in an organic solvent A, adding a diisocyanate modifier and a catalyst A, reacting at a certain temperature, continuously adding alkynyl alcohol into the solution, reacting again under stirring, and purifying after the reaction is finished to obtain alkynyl-terminated liquid silicone rubber;
(2) fully dissolving a certain proportion of alkynyl-terminated liquid silicone rubber and azido ABS in a proper amount of organic solvent B, adding catalyst B, stirring and reacting at 25-60 ℃ for 24-48h, and then purifying to obtain the cross-linked silicone rubber graft ABS copolymer.
2. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: the molar ratio of the diisocyanate modifier to the hydroxyl-terminated liquid silicone rubber in the step (1) is 2:1-3:1, and the molar ratio of the alkynyl alcohol to the diisocyanate modifier is 1:1-2: 1.
3. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: the catalyst A is selected from dibutyltin dilaurate or stannous octoate, the catalyst B is selected from cuprous chloride or cuprous bromide, the reaction temperature of the reaction between the diisocyanate modifier and the hydroxyl-terminated liquid silicone rubber in the step (1) is 50-100 ℃, and the reaction time is 12-24 hours.
4. The preparation method of the polycarbonate low-temperature toughening modifier according to any one of claims 1 to 3, wherein the method comprises the following steps: the diisocyanate modifier is any one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
5. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the molecular weight of the hydroxyl-terminated liquid silicone rubber is 10-50 ten thousand.
6. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the alkynyl-terminated liquid silicone rubber to the azide ABS in the step (2) is 2:1-4: 1.
7. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: and the preparation method also comprises the step of preparing the azide ABS, and the prepared azide ABS is stored in a dry environment at the temperature of less than 10 ℃ in a dark place.
8. The preparation method of the polycarbonate low-temperature toughening modifier according to claim 1, wherein the preparation method comprises the following steps: the purification step in the step (2) comprises the following steps:
firstly, precipitating a solid product by using excessive absolute ethyl alcohol;
and then repeatedly washing with EDTA salt solution to remove the catalyst, thus obtaining the cross-linked silicone rubber graft ABS copolymer.
9. A polycarbonate low-temperature toughening modifier is characterized in that: the cross-linked silicone rubber graft ABS copolymer prepared by the preparation method according to any one of claims 1 to 8.
10. A low-temperature toughening method for polycarbonate is characterized by comprising the following steps: adding 1-5% by mass of the cross-linked silicone rubber graft ABS copolymer prepared by the preparation method according to any one of claims 1-8 to polycarbonate.
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