CN110330659B - Splicing comb type reactive copolymer containing reactive group and preparation method and application thereof - Google Patents
Splicing comb type reactive copolymer containing reactive group and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- 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
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a splicing comb type reactive copolymer containing reactive groups, and a preparation method and application thereof. The polymer A is used as a bridging part, the molecular chain of the polymer B capable of reacting with the polymer A is used as a co-grafted long-chain molecule, and a comb-type reactive copolymer is generated in situ by using a melt processing means; wherein the polymer B is polymer B1 or mutually incompatible polymers B1 and B2, and can react with the polymer A under the condition of melt blending. Depending on the compatibilized blend system, polymer B is either polymer B1 or B2 or both, and is used as a compatibilizer in B1/B2 incompatible systems, or as a compatibilizer in C/D incompatible systems, where polymer C is thermodynamically compatible with polymer B1 and polymer D is thermodynamically compatible with polymer B2. The system after being compatibilized by the compatibilizer shows excellent mechanical properties.
Description
Technical Field
The invention relates to the field of high polymer materials, and relates to a spliced comb-shaped reactive copolymer containing reactive groups, a preparation method and application thereof, in particular to a comb-shaped reactive copolymer prepared by melt blending.
Background
The polymer alloy is the most effective method for preparing the novel polymer material, and has the following advantages: (1) the development period is short, and the cost is low; (2) effectively improve the performance of the polymer to obtain the material with excellent performance. However, unlike small molecules, most of the polymers are difficult to be mixed with each other to obtain a compatible system, which results in phase separation on a macroscopic scale, and the performance of the material is even worse than that of a single component, thus greatly hindering the development of novel materials.
The method for solving the compatibility between macromolecules is to add a compatilizer into an incompatible system, wherein the compatilizer is generally divided into a reactive compatilizer and a non-reactive compatilizer, the non-reactive compatilizer is generally added into the incompatible system by using a block polymer or a graft polymer synthesized in advance, and the compatibilization effect is achieved through the action of a non-covalent bond. However, the reactive compatibilizers generate the graft or block copolymers in situ upon addition to the blend, thereby compatibilizing the incompatible system. Reactive compatibilizers are reported in the literature to have better compatibilization effects on incompatible polymer systems than non-reactive compatibilizers, and therefore reactive compatibilizers are generally used in the industry to improve the compatibility of incompatible systems. The reactive compatibilizers generally have a linear structure and form a single graft polymer during melt blending. Because of the asymmetric structure of the single-graft copolymer, the single-graft copolymer is easy to be pulled into and pulled out of an interface under the shearing condition, and micelles are formed in a matrix, so that the performance of the material is damaged.
In order to solve the problems, a method for splicing a comb-type reactive copolymer is provided, and the prepared comb-type reactive copolymer is subjected to grafting reaction in melt blending. The graft copolymer can be stably positioned on an interface to achieve the effect of high-efficiency compatibilization. The method of the invention also overcomes the defect that most of the existing comb-type reactive compatibilizers are prepared by adopting a complex chemical synthesis method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops a novel preparation method of a comb-type reactive copolymer, and particularly discloses a method for preparing the comb-type reactive copolymer by melt blending.
The comb-type copolymer is a polymer B which takes a polymer A as a bridging part and can react with the polymer A, and a molecular chain of the polymer B is taken as a co-grafted long-chain molecule, and the comb-type reactive copolymer is generated in situ by means of melt processing; different grafting rates, different grafting contents and different grafting lengths; wherein the polymer B is one or two of mutually incompatible polymers B1 and B2, and can react with the polymer A under the condition of melt blending;
the polymer A is a linear structure, and active reactive groups capable of reacting with the polymer B are randomly distributed on the main chain of the polymer A; the number average molecular weight range is 3000-50000, and the mass content of active reaction groups is 10% -90%; preferably, the backbone includes, but is not limited to, polystyrene, polymethylmethacrylate, polybutylmethacrylate, or nanoparticles; reactive groups include, but are not limited to, epoxy groups, maleic anhydride groups;
the polymer B reacts with the active reactive group of the polymer A under the condition of melt blending, and the number average molecular weight of the polymer B is 5000-100000.
Another subject of the invention is the use of the abovementioned comb-reactive copolymers as compatibilizers for B1/B2 incompatible systems, or as compatibilizers for C/D incompatible systems, where polymer C is thermodynamically compatible with polymer B1 and polymer D is thermodynamically compatible with polymer B2.
Preferably, the comb-reactive copolymer of the present invention accounts for 0.3% to 9% of the total mass.
The invention also aims to provide a preparation method of the comb-type reactive copolymer, which is to add excessive polymer A and polymer B into a melt mixing device for melt blending; the polymer B can perform grafting chemical reaction with the active reaction group in the polymer A to form a comb-shaped reactive copolymer.
The reactive groups in polymer a are more reactive than the reactive groups in polymer B.
The melt blending processing temperature is 160-250 ℃.
The melt-kneading equipment may be any of various melt-kneading apparatuses commonly used in industry, such as an internal mixer, a single-screw extruder, a twin-screw extruder, or an injection machine.
In order to obtain a fully grafted comb-type reactive copolymer, sufficient melt blending is required in melt blending, which means that sufficient reaction of polymer B with polymer a is achieved, which requires the use of higher rotational speeds and sufficient reaction times. If the melting and mixing device is an internal mixer, the rotating speed of the internal mixer is usually 50-100 rpm, and the mixing time is 10-15 min. If the melt kneading equipment is a twin-screw extruder, the screw speed of the extruder is 100 to 200 rpm.
The invention has the advantages that (1) the polymer A with the reactive group is simple to prepare; (2) the polymer B is a common macromolecule; (3) the preparation only needs common melting and mixing equipment, and the industrial preparation is simple; (4) the system after being compatibilized by the compatibilizer shows excellent mechanical properties.
Drawings
FIG. 1a is a TEM image of a sample of comparative example 1, FIG. 1b is a TEM image of a sample of comparative example 2, and FIG. 1c is a TEM image of a sample of example 1.
FIG. 2 is a graph of notched impact strength for comparative examples 1, 2 and example 1.
Fig. 3 is a stress-strain graph of comparative examples 1, 2 and example 1.
Detailed Description
For further understanding of the present invention, the present invention will be further described with reference to the following examples, but the scope of the present invention is not limited thereto.
The polylactic acid material used in the following examples was manufactured by Nature corporation, USA, and the trade name is 3001D; the copolymer of butylene adipate and butylene terephthalate used was Poly (butylene-adipate-co-terephthalate) (PBAT), a sample supplied by Yifan Fuxin responsibility Co., Ltd., under the trade name Biocosafee 2003.
The materials obtained in the examples were used to prepare 80mm × 10mm × 4mm strip-shaped specimens by using a micro injection molding machine, and then notched 2mm by using a notch sampling machine, left for 24 hours before the test, and tested by using the standard HG/T3841-2006.
Tensile properties were measured according to ASTM D412-80 with an Instron-5966 tensile tester at a tensile speed of 5 mm/min. The tensile test was carried out in an environment at a temperature of 25 ℃ and a relative humidity of 50%.
Comparative example 1
The copolymer of the polybutylene adipate and the polybutylene terephthalate and the polylactic acid are mixed and stirred at room temperature according to the proportion of 50:50, then the mixture is added into an internal mixer, the temperature of the internal mixer is 190 ℃, the set rotating speed is 50rpm, and the mixture is discharged after internal mixing for 10 minutes. The above mixed sample was injection molded by a micro injection molding machine to prepare a standard test specimen for performance test, and the results are shown in table 1.
Comparative example 2
(1) Preparation of copolymer of styrene-glycidyl methacrylate Poly (styrene-co-glycidyl methacrylate) (SG): styrene-glycidyl methacrylate, styrene and azoisobutyronitrile were dissolved in toluene, and chemical reaction was performed by exhausting gas through nitrogen. And diluting the product obtained after the reaction is stopped with acetone, and precipitating twice with petroleum ether to obtain the styrene-glycidyl methacrylate copolymer SG. The number average molecular weight of SG is 3000-50000, and the mass content of active reaction groups is 10% -90%.
(2) Mixing and stirring polylactic acid, a copolymer of polybutylene adipate and polybutylene terephthalate and a copolymer SG of styrene-glycidyl methacrylate at a ratio of 50:50:3 at room temperature, adding the mixture into an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the set rotating speed is 50rpm, and internally mixing for 10 minutes and then discharging. The above mixed sample was injection molded by a micro injection molding machine to prepare a standard test specimen for performance test, and the results are shown in table 1.
Example 1
(1) Preparation of copolymer of styrene-glycidyl methacrylate Poly (styrene-co-glycidyl methacrylate) (SG): styrene-glycidyl methacrylate, styrene and azoisobutyronitrile were dissolved in toluene and chemical reaction was carried out by exhausting gas through nitrogen. And diluting the product obtained after the reaction is stopped with acetone, and precipitating twice with petroleum ether to obtain the styrene-glycidyl methacrylate copolymer SG. The number average molecular weight of SG is 3000-50000, and the mass content of active reaction groups is 10% -90%.
(2) Respectively drying the copolymer of the butylene adipate and the butylene terephthalate with the number average molecular weight of 5000-100000 and the copolymer SG of the styrene-glycidyl methacrylate in a vacuum oven at 80 ℃ for 24 hours, and then, according to the mass ratio of the copolymer of the butylene adipate and the butylene terephthalate to the copolymer of the styrene-glycidyl methacrylate, 40:20 at room temperature, was mixed and stirred and then charged into an internal mixer at 190 ℃ and set at 50rpm for a mixing time until the torque did not rise, and the comb-type reactive polymer was designated as S1B 2.
(3) Taking out a part of the sample obtained by the preparation, adding the part into a PLLA and PBAT blending system, keeping the mass ratio of PLLA to PBAT to S1B2 constant at 50:44:9, and carrying out melt blending in an internal mixer, wherein the temperature of the internal mixer is 190 ℃, the set rotation speed is 50rpm, and the mixing time is 10 minutes.
(4) And (3) performing injection molding on the mixed sample by a micro injection molding machine (the temperature of an injection molding barrel is 200 ℃, the temperature of a mold is 50 ℃) to obtain a dumbbell-shaped sample strip and an impact sample strip, and making the impact sample strip into a notch. The results of the experiment are shown in table 1. The above mixed sample was injection molded by a micro injection molding machine to prepare a standard test specimen for performance test, and the results are shown in table 1.
Table 1: mechanical properties of PLLA/PBAT alloy
As can be seen from Table 1, the transmission of example 1, comparative example 1 and comparative example 2 is characterized in FIG. 1, with PLLA being the white phase and PBAT the black phase. PLLA is a dispersion phase distributed in the PBAT matrix phase, the dispersion phase shows a large phase region without compatibilizer (comparative example 1), and when the styrene-glycidyl methacrylate copolymer (SG) is added to the PLLA/PBAT blend system, the phase region of PLLA is significantly reduced compared to the non-compatibilized system (comparative example 2). However, many black micelles appear in the PLLA phase, and this micelle is considered as a compatibilizer. When the comb-type reactive compatibilizer S1B2 of this example 1 was added to the PLLA/PBAT system, it can be seen that the morphology of the blend changed to a bicontinuous structure, and the micelles in the PLLA phase were significantly reduced. The comb-type reactive copolymer prepared by melt blending has good compatibilization effect on a PLLA/PBAT incompatible blending system.
FIG. 2 is a graph of notched impact strength for comparative examples 1, 2 and example 1, and FIG. 3 is a graph of stress-strain curves for comparative examples 1, 2 and example 1.
Example 2:
(1) respectively drying a copolymer (PBAT) of butylene adipate and butylene terephthalate with the number average molecular weight of 5000-100000 and a copolymer (MH) of maleic anhydride-glycidyl methacrylate in a vacuum oven at 80 ℃ for 24 hours, mixing and stirring the mixture according to the ratio of PBAT to MH of 2:1 at room temperature, adding the mixture into an internal mixer, wherein the temperature of the internal mixer is 180 ℃, the set rotating speed is 100rpm, and the mixing time is that the torque does not rise any more, so that the comb-type reactive polymer is recorded as M1B 2. MH number average molecular weight is 3000-50000, and the mass content of active reaction groups is 10-90%.
(2) Taking out a part of the sample obtained by the preparation, adding the part into a PLLA and PBAT blending system, keeping the mass ratio of PLLA to PBAT to MH constant at 50:50:3, and carrying out melt blending in an internal mixer, wherein the temperature of the internal mixer is 180 ℃, the set rotating speed is 100rpm, and the mixing time is 10 minutes. The final product has a notch impact strength of 80.1kJ/m2The tensile strength can reach 29MPa, and the performance is far higher than that of a PLLA/PBAT/MH system which is only compatibilized by a linear compatibilizer.
Example 3:
(1) respectively drying Polycarbonate (PC) with the number average molecular weight of 5000-100000 and polymethyl methacrylate (PMMA) with terminal carboxyl groups with the number average molecular weight of 4000 and nano particles (NG) with reactive epoxy groups in a vacuum oven at 80 ℃ for 24 hours, mixing and stirring at room temperature according to the proportion of PC to NG to PMMA of 1:1:1, adding into an internal mixer, setting the temperature of the internal mixer at 230 ℃, setting the rotating speed at 100rpm, and mixing for a time when the torque is not increased, wherein the comb-type reactive polymer is marked as M1N1C 1. The range of the number average molecular weight of NG is 3000-50000, and the mass content of the active reaction group is 10-90%.
(2) Taking out a part of the prepared sample, adding the part into a blending system of polyvinylidene fluoride (PVDF) and PBAT, keeping PVDF, PBAT, M1N1C1, 47 and 9, and carrying out melt blending in an internal mixer, wherein the temperature of the internal mixer is 230 ℃, the set rotating speed is 150rpm, and the mixing time is 10 minutes.
Since polycarbonate PC and PBAT have good compatibility, PMMA and PVDF are completely thermodynamically compatible, and PC grafted onto nanoparticlesWith sufficient entanglement with the PBAT phase, PMMA can interact with PVDF. The final product therefore had a notched impact strength of 69.1kJ/m2The tensile strength reaches 30 MPa.
Example 4:
(1) respectively drying Polycarbonate (PC) with the number average molecular weight of 5000-100000 and styrene-glycidyl methacrylate copolymer SG in a vacuum oven at 80 ℃ for 24 hours, mixing and stirring at room temperature according to the proportion of PC to SG of 30:30, and adding into a double-screw extruder at the temperature of 180 ℃,210 ℃,210 ℃ and 190 ℃. The rotation speed was set at 150rpm, and the comb-type reactive polymer produced was designated as S1C 1. The number average molecular weight of SG is 3000-50000, and the mass content of active reaction groups is 10% -90%.
(2) Taking out a part of the sample obtained by the preparation, adding the part into a PLLA and PC blending system, keeping the mass ratio of PLLA to PC to SG at 50:50:1, and carrying out melt blending in a double-screw extruder at the temperature of 180 ℃,210 ℃,210 ℃,190 ℃ and the set rotating speed of 150 rpm.
The notch impact strength of a final product obtained by double-screw extrusion reaches 15kJ/m2The tensile strength reaches 66MPa, and the performance of the blend system is far better than that of an uncompatibilized PC/PLLA blend system.
Example 5:
(1) the copolymer (PBAT) of butylene adipate and butylene terephthalate with a longer molecular chain structure is longer than that of the PBAT in all the examples, the number average molecular weight is 5000-200000, and the copolymer SG of styrene-glycidyl methacrylate is dried in a vacuum oven at 80 ℃ for 24 hours respectively, mixed and stirred at room temperature according to the proportion of PBAT: SG being 40:20, and then added into an internal mixer, the temperature is 180 ℃, the set rotating speed is 50rpm, and the prepared comb-type reactive polymer is marked as S1B 2. The number average molecular weight of SG is 3000-50000, and the mass content of active reaction groups is 10% -90%.
(2) Taking out a part of the prepared sample, adding the part into a PLLA and PBAT blending system, keeping the mass ratio of PLLA to PBAT to SG at 50:50:3, and carrying out melt blending in an internal mixer at the temperature of 180 ℃ and the set rotating speed of 50 rpm. Impact of the resulting productThe strength reaches 89kJ/m2The tensile strength was 31 MPa.
Claims (5)
1. Use of a "split-end" comb reactive copolymer containing reactive groups as a compatibilizer for polymer B1/polymer B2 incompatible systems or polymer C/polymer D incompatible systems, said polymer C being thermodynamically compatible with polymer B1 and polymer D being thermodynamically compatible with polymer B2; the method is characterized in that the spliced comb-type reactive copolymer containing the reactive groups is a comb-type reactive copolymer generated in situ by using a melt processing means by taking a polymer A as a bridging part and taking a molecular chain of a polymer B as a co-grafted long-chain molecule; wherein the polymer B is one or two of mutually incompatible polymers B1 and B2, and can react with the polymer A under the condition of melt blending;
the polymer A is a linear structure, and active reaction groups capable of reacting with the polymer B are randomly distributed on the main chain of the polymer A; the number average molecular weight range is 3000-50000, and the mass content of active reaction groups is 10% -90%;
the main chain of the polymer A is polystyrene, polymethyl methacrylate or polybutyl methacrylate; the active reaction group is an epoxy group or a maleic anhydride group;
the reactive groups in polymer a are more reactive than the reactive groups in polymer B.
2. The use according to claim 1, wherein the polymer B has a number average molecular weight of 5000 to 100000.
3. Use according to claim 1, wherein the "spliced" comb-type reactive copolymer containing reactive groups is prepared by: adding the polymer B and the polymer A into a melt mixing device for melt blending; the polymer B and the active reaction group in the polymer A generate a grafting chemical reaction in situ to form a comb-shaped reactive copolymer;
the polymer B is one or two of mutually incompatible polymers B1 and B2, and can react with the polymer A under the condition of melt blending;
the melt blending processing temperature is 160-250 ℃.
4. The use according to claim 3, wherein the melt-mixing device is an internal mixer, a single screw extruder, a twin screw extruder or an injection machine; if the melting and mixing device is an internal mixer, the rotating speed of the internal mixer is 50-100 rpm, and the mixing time is 10-15 min; if the melting and mixing equipment is a double-screw extruder, the screw rotating speed of the extruder is 100-200 rpm.
5. Use according to claim 1, wherein the "spliced" comb-reactive copolymer represents from 0.3% to 9% by mass of the polymer B1/polymer B2 incompatible system or the polymer C/polymer D incompatible system.
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