CN111073160A - 3D printing high-performance polypropylene composite material and preparation method thereof - Google Patents
3D printing high-performance polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a 3D printing high-performance polypropylene composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: polypropylene, nylon elastomer, filler, compatilizer, adhesive and antioxidant. The composite material has low shrinkage, low warpage, high strength, high toughness, excellent surface gloss and good heat resistance. The 3D printing wire rod can be prepared from the composite material by a melt blending extrusion method, and the printed product has good dimensional accuracy and appearance quality.
Description
Technical Field
The invention belongs to the field of 3D printing materials, and particularly relates to a 3D printing high-performance polypropylene composite material and a preparation method thereof.
Background
The most common 3D printing materials of FDM technology in the market at present are ABS, PLA, TPE, etc. The ABS has the characteristics of light weight, good mechanical property, slight toughness, easiness in extrusion and the like, is widely applied to industrial-grade 3D printing, has a high melting point, generates unpleasant and toxic gases during printing, and needs to be placed in an environment with good ventilation or a closed box and an air purification device; PLA is a degradable and renewable environment-friendly material, does not generate toxic and unpleasant gas during melting, but has poor heat resistance and mechanical property, is easy to generate brittle fracture, and greatly limits the use of printed objects. TPE materials have good elasticity, can prepare products with good extensibility, but have the defects of high printing difficulty, difficulty in controlling feeding and the like.
Polypropylene (PP) has the advantages of low density, high strength, heat resistance, good insulation, low cost, excellent chemical stability, etc., is one of general-purpose plastics widely studied and applied, and is popular in the fields of household appliances, automobiles, plastic pipes, etc. However, PP has the disadvantages of poor impact resistance, poor toughness, large molding shrinkage, and the like, and has limitations in application of 3D printing due to problems of deformation and warpage caused by easy shrinkage of products, brittle products, poor dimensional accuracy, rough appearance, and the like during 3D printing.
Disclosure of Invention
The invention aims to provide a high-performance polypropylene composite material for 3D printing, which has the excellent performances of polypropylene and an added modified material, is high in safety, and particularly has high strength, high modulus, low shrinkage and warpage, excellent thermal stability and appearance quality. The material is used as a raw material of a wire rod for 3D printing, has very good printing precision and printing effect, has high bonding strength between layers of a product, has low smell, can meet the actual requirement of 3D printing, and has a simple wire rod preparation process.
In order to achieve the above purpose and achieve the above technical effects, the technical solution of the present invention is as follows:
A3D printing high-performance polypropylene composite material is prepared from the following raw materials:
wherein the mass parts of the nylon elastomer and the adhesive are not 0 at the same time.
In the present invention, the polypropylene is selected from one or more of an ethylene-propylene random copolymer, an ethylene-propylene block copolymer, a copolymerized polypropylene containing an ethylene-propylene random copolymer, and a copolymerized polypropylene containing an ethylene-propylene block copolymer.
In the invention, the melt flow index of the polypropylene at 2.16kg and 230 ℃ is 15-40 g/10min, preferably 25-32 g/10 min.
In the invention, the nylon elastomer is a polyamide block copolymer.
In the present invention, the soft segment of the polyamide block copolymer is selected from one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetrahydrofuran glycol, copolyether glycol, polyether diamine, polyester, polycarbonate, polyolefin and polysiloxane, and preferably the soft segment is polyethylene glycol and/or polytetramethylene glycol.
In the invention, the hard segment of the polyamide block copolymer is selected from one or more of PA6, PA46, PA66, PA11, PA610, PA12, PA1010, PA1212, PA6/11 copolymer, PA6/12 copolymer, aromatic polyamide and semi-aromatic polyamide, and the hard segment is preferably PA11 and/or PA 12.
In the present invention, the Shore hardness of the polyamide block copolymer is 20 to 70D, preferably 25 to 50D.
In the present invention, the filler is selected from one or more of talc, calcium carbonate and mica.
In the present invention, the compatibilizer is one or more selected from the group consisting of an epoxy-type compatibilizer, a carboxylic acid-type compatibilizer, and an acid anhydride-type compatibilizer, preferably an acid anhydride-type compatibilizer, and more preferably maleic anhydride-grafted polypropylene.
In the present invention, the adhesive is one or more of ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), and dopamine graft acrylic acid-acrylate copolymer, and is preferably an adhesive or an adhesive composition containing at least dopamine graft acrylic acid-acrylate copolymer. The addition of the adhesive can improve the interface effect of polypropylene and the nylon elastomer on one hand, and can improve the bonding effect between layers of the product in the 3D printing process and improve the bonding strength of the product on the other hand. Compared with the existing commercial adhesive, the adhesion performance of the dopamine grafted acrylic acid-acrylate copolymer is greatly improved. Meanwhile, the specific catechol structure has numerous chemical functionalities and affinity diversity, so that the adhesive has good adhesive effect on polymers, glass, metal and other materials. When carrying out first layer printing on the 3D printer, can increase the bonding of plastics and print table, and then effectively reduce the warpage phenomenon.
In the invention, the structure of the repeating unit of the dopamine grafted acrylic acid-acrylate copolymer is as follows:
wherein R is C1-C8 alkyl, preferably R is C1-C4 alkyl, x is the number of repeating units of acrylic acid, y is the number of repeating units of acrylic ester, Mw is 5000-300,000, preferably Mw is 10,000-300,000.
In the invention, the grafting rate of the dopamine grafted acrylic acid-acrylate copolymer is 40-99%. The grafting ratio is the ratio of the total mass of dopamine grafted onto the copolymer molecules to the total mass of copolymer dosed.
In the invention, the dopamine grafted acrylic acid-acrylate copolymer is a random copolymer or a block copolymer.
In the invention, the main chain acrylic acid-acrylate copolymer of the dopamine grafted acrylic acid-acrylate copolymer is formed by free radical polymerization of acrylic acid and acrylate.
In some embodiments, the acrylic acid-acrylate copolymer is prepared by: under the protection of nitrogen, sequentially adding acrylic acid, acrylic ester, azodiisobutyronitrile and ethanol into a reaction bottle, heating to 50-80 ℃, reacting for 8-16h, settling in n-hexane, repeatedly settling with n-hexane/ethanol for multiple times until supernatant is colorless, and vacuum drying to obtain the product.
In the invention, the preparation method of the dopamine grafted acrylic acid-acrylate copolymer comprises the following steps: dissolving acrylic acid-acrylate copolymer and dopamine in a solvent, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine for reaction, and after the reaction is finished, washing and drying reaction liquid to obtain a product.
In the invention, the solvent is a mixed solution of dichloromethane and dimethylformamide.
In the invention, the reaction temperature for preparing the dopamine grafted acrylic acid-acrylate copolymer is room temperature, and the reaction time is 12-24 h.
In the invention, the reaction liquid prepared by the dopamine grafted acrylic acid-acrylate copolymer is washed by normal hexane and is dried for 24-48h under vacuum at the temperature of 30-50 ℃.
In the present invention, the antioxidant is selected from one or more of hindered phenol antioxidants, phosphorous antioxidants and alkyl ester antioxidants, and is preferably a mixture of hindered phenol antioxidants and phosphite antioxidants.
In the invention, when the dopamine grafted acrylic acid-acrylate copolymer and the nylon elastomer are respectively and independently added, the performance of the composite material can be improved; when the additive is added at the same time, a synergistic effect is generated, and the performance of the composite material is further improved, because the catechol group in the dopamine graft copolymer can form a very strong complex bond with metal ions, the dispersion and mixing effect of the filler in the composite material is improved; meanwhile, as phenolic hydroxyl is a group with strong polarity, the phenolic hydroxyl can form hydrogen bonds with nylon elastomer and maleic anhydride grafted polypropylene, in addition, catechol structure is easy to be oxidized into ortho-diquinone, and the structure can react with active hydrogen on hydroxyl and amino to form chemical bonds, so that the compatibility of a composite material system and the cohesive force of a phase interface are improved.
Another object of the present invention is to provide a method for preparing the 3D printed high performance polypropylene composite.
A method for preparing the 3D printing high-performance polypropylene composite material.
In the invention, the preparation method comprises the following steps: and uniformly mixing the polypropylene, the optional nylon elastomer, the compatilizer, the adhesive and the antioxidant, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the polypropylene composite material.
In the present invention, the nylon elastomer is dried in advance under the condition of 80-100 ℃ for 2-6 hours, preferably 90 ℃ for 4 hours.
In the invention, the moisture mass content of the dried nylon elastomer is less than 0.1%.
In the invention, the process conditions of the double-screw extruder are as follows: the extrusion temperature is 160-; the screw rotation speed is 100-300rpm, preferably 150-250 rpm.
Still another object of the present invention is to provide a use of the 3D printed high performance polypropylene composite.
The application of the 3D printing high-performance polypropylene composite material is used in the field of 3D printing resin materials.
In the invention, when the 3D printing high-performance polypropylene composite material is used for 3D printing resin materials, various process conditions can be adopted, in some embodiments, the polypropylene composite material is added into an extruder provided with a wire extrusion die to prepare 3D printing wires, the extrusion temperature is set to be 230 ℃, the screw rotating speed is 5-30rpm, the diameter of the extrusion die is 3.00 +/-0.05 mm, the cooling water temperature is between room temperature and 70 ℃, and the wires with two current commonly used commercial specifications of 1.75 +/-0.05 mm and 3.00 +/-0.05 mm can be obtained by controlling a proper traction ratio.
In some embodiments, the prepared 3D printing consumables are printed, and printing conditions such as the thickness of the forming layer, the scanning speed, the temperature of the nozzle, the forming temperature and the like are controlled during printing.
The invention has the beneficial effects that:
(1) the 3D printing polypropylene composite material has excellent mechanical property, processability and apparent mass by adopting the nylon elastomer to toughen the polypropylene, simultaneously reduces the shrinkage deformation of the polypropylene, and improves the dimensional stability and precision of a 3D printing product, wherein the printing precision deviation is less than 1%.
(2) The addition of acrylic acid (ester) as adhesive, especially dopamine grafted acrylic acid-acrylate copolymer, can effectively improve the interfacial action between polypropylene and nylon elastomer and inorganic filler, improve the bonding strength of printed products, and effectively reduce the warping of products.
(3) The invention has simple production process, safety, environmental protection, low requirement on production equipment and good market application prospect.
Drawings
FIG. 1 is a diagram of the dopamine graft acrylic acid-acrylate copolymer A prepared in example 11H NMR spectrum.
Detailed Description
The invention is further described below with reference to specific examples, but the invention is not limited to the examples listed but also encompasses any known modification within the scope of the claims.
Equipment and apparatus:
twin-screw extruder, ZSK35, Keplon machines Co., Ltd,
single screw extruder, HRJ45, Hairyja precision extrusion machinery, Inc.,
3D printer, Finder, Zhejiang flash casting three-dimensional technology Co., Ltd,
nuclear magnetic resonance apparatus, MERCURY plus 400, Varian corporation,
gel permeation chromatograph, PL-GPC220, Polytech, column temperature: 35.0 ℃, flow rate: 1.0 ml/min.
Melt index apparatus, MF30, company CEAST.
Information of main raw materials:
copolymerized polypropylene (copolymerized polypropylene containing ethylene-propylene random copolymer):
the copolymer polypropylene EP548RQ, melt flow index 28g/10min, Tianjin Zhongsha petrochemical Co., Ltd,
copolypropylene K7726H, melt flow index 25g/10min, Yanshan petrochemical Co., Ltd.
Nylon elastomer (polyetheramide block copolymer of PA 12):
PEBAX2533, melt flow index 10g/10min, hardness 25D, AKEMA,
PEBAX3533, melt flow index 8g/10min, hardness 33D, AKEMA,
PEBAX4533, melt flow index 6g/10min, hardness 46D, AKEMA,
PEBAX7033, melt flow index 5g/10min, hardness 69D, AKEMA.
Adhesive:
EAA 3460, melt flow index 20g/10min, Dow chemical,
EAA 3150, melt flow index 11g/10min, Dow chemical.
Antioxidant:
irganox 1010 (hindered phenolic antioxidant), Basff,
irgafox 168 (phosphite based antioxidant), Basff,
the antioxidant is added in the form of a mixture, and the mass ratio of 1010 to 168 is 1: 1.
a compatilizer:
maleic anhydride-grafted polypropylene, Qingdao Sainuo chemical Co., Ltd.
Filling:
talc powder, Tahite, Inc., of Laizhou.
Graft raw materials:
DMA: dopamine hydrochloride, BR, 98%, Sigma-Aldrich,
EDC: 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, BR, 98%, Alfa Aesar,
HOBT: 1-hydroxybenzotriazole, BR, 99%, Alfa Aesar.
Preparing a wire and printing:
adding the obtained polypropylene composite material into a single-screw extruder to prepare FDM 3D printing consumables, controlling the extrusion temperature at 160-230 ℃, controlling the water temperature, the extrusion amount and the traction rate, controlling the diameter of the consumables to be 1.75 +/-0.05 mm, and measuring the diameter deviation and the ovality of the wire rod on line by using a diameter measuring instrument.
Printing the 3D printing supplies obtained by preparation, wherein the printing conditions are as follows: the thickness of the molding layer is 0.175mm, and the scanning speed is 40cm3And/h, the temperature of the nozzle is 200-220 ℃, the temperature of the forming chamber is 60-80 ℃, and other parameters such as scanning line width and the like are formed by adopting default parameters of the system.
And (3) testing the performance of the material:
melt flow rate: the test temperature was 230 ℃ and the test load 2.16kg were carried out in accordance with ISO 1133.
Tensile strength: the test specimens were 170 × 10 × 4mm in size and drawn at a speed of 50mm/min, according to ISO 527.
Bending strength: the test specimens were 80 x 10 x 4mm in size and the bending speed 2mm/min, carried out according to ISO 178.
Notched izod impact strength: the test specimens were 80 × 10 × 4mm in size, performed according to ISO 180.
Shrinkage rate: the test specimens were 60 × 2mm in size, performed according to ISO 294.
Grafting ratio: the ratio of the total mass of dopamine grafted onto the copolymer molecules to the total mass of copolymer dosed.
Example 1
Preparation of acrylic acid-methyl acrylate copolymer 1, 2, 3:
under the protection of nitrogen, sequentially adding 14.7g of acrylic acid, 27.1g of methyl acrylate, 0.5g of azobisisobutyronitrile and 300ml of ethanol into a reaction bottle, heating to 60 ℃, reacting for 12 hours, then settling in 600ml of n-hexane, repeatedly settling by using n-hexane/ethanol for multiple times until supernatant is colorless, and carrying out vacuum drying at 50 ℃ for 24 hours to obtain the acrylic acid-methyl acrylate copolymer 1.
Under the protection of nitrogen, 14.6g of acrylic acid, 26.7g of methyl acrylate, 1.2g of azobisisobutyronitrile and 300ml of ethanol are sequentially added into a reaction bottle, the temperature is increased to 80 ℃, the mixture reacts for 8 hours, then the mixture is settled in 600ml of n-hexane, then n-hexane/ethanol is repeatedly settled for many times until supernatant is colorless, and the mixture is dried under vacuum at 50 ℃ for 24 hours to obtain the acrylic acid-methyl acrylate copolymer 2.
Under the protection of nitrogen, 15.1g of acrylic acid, 28.5g of methyl acrylate, 0.3g of azobisisobutyronitrile and 300ml of ethanol are sequentially added into a reaction bottle, the temperature is increased to 60 ℃, the mixture reacts for 16 hours, then the mixture is settled in 600ml of n-hexane, then n-hexane/ethanol is repeatedly settled for many times until supernatant is colorless, and the mixture is dried under vacuum at 50 ℃ for 24 hours to obtain the acrylic acid-methyl acrylate copolymer 3.
Preparation of dopamine grafted acrylic acid-acrylate copolymer A, B, C, D, E:
under the protection of nitrogen, 9.82g of acrylic acid-methyl acrylate copolymer 1, 6.55g of DMA is dissolved in 320ml of dichloromethane/dimethylformamide (volume ratio is 1:1) mixed solution, 7.92g of EDC, 1.44g of HOBT and 0.34g of triethylamine are added, the mixture reacts for 15 hours at room temperature, the obtained reaction solution is repeatedly washed by normal hexane and then is dried for 24 hours under vacuum at 50 ℃, and the grafting ratio of the product A is 53 percent; the molecular weight of product A was determined to be 141,000 by GPC (leacheate DMF, standard PS). Dissolving a proper amount of product in DMSO, setting the field sweeping range to be 0-12ppm, and scanning at 400Hz to obtain a resonance hydrogen spectrum, which is shown in figure 1.
Under the protection of nitrogen, 9.84g of acrylic acid-methyl acrylate copolymer 1, 6.71g of DMA is dissolved in 320ml of dichloromethane/dimethylformamide (volume ratio is 1:1) mixed solution, 7.64g of EDC, 1.36g of HOBT and 0.32g of triethylamine are added, the reaction is carried out for 12h at room temperature, the obtained reaction solution is repeatedly washed by normal hexane and then is dried under vacuum at 50 ℃ for 24h, and the grafting ratio of the product B is 46 percent; the molecular weight of product B was determined by GPC (leacheate DMF, standard PS) to be 134,000.
Under the protection of nitrogen, 9.72g of acrylic acid-methyl acrylate copolymer 1, 6.63g of DMA is dissolved in 320ml of dichloromethane/dimethylformamide (volume ratio is 1:1) mixed solution, 8.04g of EDC, 1.56g of HOBT and 0.36g of triethylamine are added for reaction at room temperature for 24 hours, the obtained reaction solution is washed by n-hexane and then is dried under vacuum at 50 ℃ for 24 hours, and the grafting ratio of the obtained product C is 64 percent; the molecular weight of product C was determined by GPC (leacheate DMF, standard PS) to be 149,000.
Under the protection of nitrogen, 9.86g of acrylic acid-methyl acrylate copolymer 2 and 9.9g of DMA are dissolved in 320ml of dichloromethane/dimethylformamide (volume ratio is 1:1) mixed solution, 7.74g of EDC, 1.46g of HOBT and 0.32g of triethylamine are added, the mixture reacts for 15 hours at room temperature, the obtained reaction solution is washed by n-hexane and then is dried for 24 hours under vacuum at 50 ℃, and the grafting rate of the obtained product D is 97 percent; the molecular weight of product D was determined to be 16,000 by GPC (leacheate DMF, standard PS).
Under the protection of nitrogen, 10.92g of acrylic acid-methyl acrylate copolymer 3 and 14.6g of DMA are dissolved in 320ml of dichloromethane/dimethylformamide (volume ratio is 1:1) mixed solution, 8.46g of EDC, 1.71g of HOBT and 0.44g of triethylamine are added, the mixture reacts for 24 hours at room temperature, the obtained reaction solution is washed by n-hexane and then is dried for 24 hours under vacuum at 50 ℃, and the grafting ratio of the obtained product E is 84%; the molecular weight of the product E was determined by GPC (leacheate DMF, standard PS) to be 294,000.
Examples 2 to 11
Drying the nylon elastomer at 90 ℃ for 4 hours to ensure that the moisture content is less than 0.1 percent; according to the proportion of each example in the table 1, polypropylene, dried nylon elastomer, compatilizer, adhesive and antioxidant are respectively and uniformly mixed, added into a main feeding hopper of a double-screw extruder with the diameter of 35mm and the length-diameter ratio of 52, added with filler into a side feeding hopper, and mixed and granulated by setting the extrusion temperature and the screw rotating speed (shown in the table 1) of each zone, so as to obtain the high-performance polypropylene composite material. Test samples of the composite material were prepared and tested for performance, the results are shown in table 2.
Adding the polypropylene composite material into an extruder provided with a wire extrusion neck ring mold to prepare a 3D printing wire, setting the extrusion temperature to be 180-. Physical properties of the wire are shown in Table 2.
Printing the 3D printing supplies obtained by preparation, wherein the printing conditions are as follows: the thickness of the molding layer is 0.175mm, and the scanning speed is 40cm3And/h, the nozzle temperature is 210 ℃, the forming temperature is 70 ℃, and other parameters such as scanning line width and the like are formed by adopting default parameters of the system. Physical properties of 3D printed sample are shown in table2。
Comparative example 1
Compare with example 4.
Preparing a polypropylene composite material: according to the proportion shown in the table 1, polypropylene, a compatilizer, a filler and an antioxidant are uniformly mixed, the mixture is added into a main feeding hopper of a double-screw extruder with the diameter of 35mm and the length-diameter ratio of 52, the filler is added into a side feeding hopper, and the extrusion temperature and the screw rotating speed (shown in the table 1) of each zone are set for mixing and granulation, so that the polypropylene composite material is obtained. Test samples of the composite material were prepared and tested for performance, the results are shown in table 2.
The wire preparation and 3D printing process parameters were the same as in example 4. The wire physical properties and 3D printed sample physical properties are shown in table 2.
Comparative example 2
Composite preparation and wire preparation were carried out according to example 1 of patent application CN 201910784698.3. 3D printing was performed as in example 2.
The composite, wire physical properties, and 3D printed sample physical properties are shown in table 2.
TABLE 1 examples 2-9 and comparative example 1 formulations and extrusion Process
TABLE 2 results of Performance test of examples 2-11 and comparative examples 1-2
As can be seen from the comparison between the examples and the comparative examples, the polypropylene composite material prepared by the formula and the process has high tensile strength, flexural modulus, notch impact strength, small dimensional deviation and ovality, and excellent physical and mechanical properties and printing performance. The material is used as a raw material of a wire rod for 3D printing, has very good printing precision and printing effect, has high bonding strength between layers of a product, has low smell, can meet the actual requirement of 3D printing, and has a simple wire rod preparation process.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (14)
1. The 3D printing high-performance polypropylene composite material is characterized by being prepared from the following raw materials:
wherein the mass parts of the nylon elastomer and the adhesive are not 0 at the same time.
2. The composite material according to claim 1, wherein the polypropylene is selected from one or more of ethylene-propylene random copolymer, ethylene-propylene block copolymer, copolymerized polypropylene containing ethylene-propylene random copolymer, and copolymerized polypropylene containing ethylene-propylene block copolymer;
and/or the melt flow index of the polypropylene at 2.16kg and 230 ℃ is 15-40 g/10min, preferably 25-32 g/10 min.
3. The composite material according to claim 1 or 2, characterized in that the nylon elastomer is a polyamide block copolymer;
and/or the soft segment of the polyamide block copolymer is selected from one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetrahydrofuran glycol, copolyether glycol, polyether diamine, polyester, polycarbonate, polyolefin and polysiloxane, and the soft segment is preferably polyethylene glycol and/or polytetramethylene glycol;
and/or the hard segment of the polyamide block copolymer is selected from one or more of PA6, PA46, PA66, PA11, PA610, PA12, PA1010, PA1212, PA6/11 copolymer, PA6/12 copolymer, aromatic polyamide and semi-aromatic polyamide, and the hard segment is preferably PA11 and/or PA 12;
and/or the polyamide block copolymer has a shore hardness of 20 to 70D, preferably 25 to 50D.
4. A composite according to any of claims 1-3, characterized in that the filler is selected from one or more of talc, calcium carbonate and mica.
5. Composite according to any one of claims 1 to 4, characterized in that the compatibilizer is selected from one or more of epoxy-type compatibilizers, carboxylic acid-type compatibilizers and anhydride-type compatibilizers, preferably anhydride-type compatibilizers, more preferably maleic anhydride grafted polypropylene.
6. The composite material according to any of claims 1 to 5, wherein the binder is one or more of ethylene acrylic acid copolymer (EAA), ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), ethylene methyl acrylate copolymer (EMA) and dopamine grafted acrylic acid-acrylate copolymer, preferably a binder or binder composition comprising at least dopamine grafted acrylic acid-acrylate copolymer.
7. The composite material of claim 6, wherein the dopamine-grafted acrylic acid-acrylate copolymer repeating units have the structure:
wherein R is C1-C8 alkyl, preferably R is C1-C4 alkyl, x is the number of repeating units of acrylic acid, y is the number of repeating units of acrylic ester, Mw is 5000-300,000, preferably Mw is 10,000-300,000.
8. Composite according to claim 6 or 7, characterized in that the grafting ratio of the dopamine grafted acrylic-acrylate copolymer is between 40 and 99%.
9. The composite material according to any of claims 6-8, wherein the dopamine grafted acrylic acid-acrylate copolymer is a random copolymer or a block copolymer;
and/or the main chain acrylic acid-acrylate copolymer of the dopamine grafted acrylic acid-acrylate copolymer is formed by free radical polymerization of acrylic acid and acrylate;
and/or the preparation method of the dopamine grafted acrylic acid-acrylate copolymer comprises the following steps: dissolving acrylic acid-acrylate copolymer and dopamine in a solvent, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and triethylamine for reaction, and after the reaction is finished, washing and drying reaction liquid to obtain a product;
and/or the solvent is a mixed solution of dichloromethane and dimethylformamide;
and/or the reaction temperature is room temperature, and the reaction time is 12-24 h.
10. Composite according to any of claims 1 to 9, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphorous antioxidants and alkyl ester antioxidants, preferably a mixture of hindered phenolic antioxidants and phosphite antioxidants.
11. A method of making the 3D printed high performance polypropylene composite of any one of claims 1 to 10.
12. The method according to claim 11, wherein the method comprises: uniformly mixing polypropylene, optional nylon elastomer, compatilizer, adhesive and antioxidant, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain a polypropylene composite material;
and/or, the nylon elastomer needs to be dried in advance, and the drying condition is that the nylon elastomer is dried for 2 to 6 hours at the temperature of between 80 and 100 ℃, and is preferably dried for 4 hours at the temperature of between 90 ℃;
and/or the water content of the dried nylon elastomer is less than 0.1 percent.
13. The method for preparing as claimed in claim 11 or 12, wherein the twin-screw extruder has process conditions of: the extrusion temperature is 160-; the screw rotation speed is 100-300rpm, preferably 150-250 rpm.
14. Use of the 3D printing high-performance polypropylene composite material according to any one of claims 1 to 10 or the 3D printing high-performance polypropylene composite material prepared by the preparation method according to any one of claims 11 to 13, in the field of 3D printing resin materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112519287A (en) * | 2020-10-22 | 2021-03-19 | 广西特斯途汽车科技有限公司 | Anti-exposure and anti-aging automobile charging pile shell |
| EP4206236A1 (en) * | 2021-12-28 | 2023-07-05 | Kao Corporation | Compounds, their synthesis and compositions comprising the compounds for enhanced deposition of polymers onto hair surfaces |
| CN114437491B (en) * | 2020-10-20 | 2023-11-10 | 中国石油化工股份有限公司 | Polypropylene wood-plastic composite material and preparation method and application thereof |
| CN117362755A (en) * | 2023-10-12 | 2024-01-09 | 广州工程技术职业学院 | Modified filler, polypropylene composite material for 3D printing and preparation method of polypropylene composite material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3805377A1 (en) * | 1988-02-20 | 1989-08-31 | Basf Ag | THERMOPLASTIC POLYPROPYLENE-POLYAMIDE MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US5179164A (en) * | 1988-02-20 | 1993-01-12 | Basf Aktiengesellschaft | Thermoplastic polypropylene/polyamide molding composition |
| US5346773A (en) * | 1989-01-12 | 1994-09-13 | Solvay & Cie (Societe Anonyme) | Adhesive composites and articles containing compatibilized composition comprising a polyamide and a polypropylene |
| CN103483680A (en) * | 2012-06-12 | 2014-01-01 | 中国科学院化学研究所 | Polypropylene long-carbon-chain nylon blend and preparation method thereof |
| CN106905600A (en) * | 2015-12-22 | 2017-06-30 | 上海邦中高分子材料有限公司 | A kind of 3D printing modified polypropylene composite material and preparation method thereof |
| CN107304271A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | One kind is based on polyacrylic composite and its preparation method and application |
| CN107813498A (en) * | 2016-09-13 | 2018-03-20 | 科思创德国股份有限公司 | Elastomeric polymer is used for the purposes for manufacturing porous body in increasing material manufacturing method |
-
2020
- 2020-01-02 CN CN202010002428.5A patent/CN111073160B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3805377A1 (en) * | 1988-02-20 | 1989-08-31 | Basf Ag | THERMOPLASTIC POLYPROPYLENE-POLYAMIDE MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US5179164A (en) * | 1988-02-20 | 1993-01-12 | Basf Aktiengesellschaft | Thermoplastic polypropylene/polyamide molding composition |
| US5346773A (en) * | 1989-01-12 | 1994-09-13 | Solvay & Cie (Societe Anonyme) | Adhesive composites and articles containing compatibilized composition comprising a polyamide and a polypropylene |
| CN103483680A (en) * | 2012-06-12 | 2014-01-01 | 中国科学院化学研究所 | Polypropylene long-carbon-chain nylon blend and preparation method thereof |
| CN106905600A (en) * | 2015-12-22 | 2017-06-30 | 上海邦中高分子材料有限公司 | A kind of 3D printing modified polypropylene composite material and preparation method thereof |
| CN107304271A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | One kind is based on polyacrylic composite and its preparation method and application |
| CN107813498A (en) * | 2016-09-13 | 2018-03-20 | 科思创德国股份有限公司 | Elastomeric polymer is used for the purposes for manufacturing porous body in increasing material manufacturing method |
Non-Patent Citations (5)
| Title |
|---|
| 中国感光学会: "《2016-2017 感光影像学 学科发展报告》", 31 March 2018, 中国科学技术出版社 * |
| 张峰 等: "多巴胺改性聚丙烯酸酯的合成及性能研究", 《材料研究与应用》 * |
| 彭治汉 等: "《塑料工业手册 聚酰胺》", 30 November 2001, 化学工业出版社 * |
| 李钟猛: "《 塑料产品设计与制造简明手册》", 28 February 1994, 西安电子科技大学出版社 * |
| 闫春泽 等: "《高分子材料3D打印成形原理与实验》", 30 June 2019, 华中科技大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437491B (en) * | 2020-10-20 | 2023-11-10 | 中国石油化工股份有限公司 | Polypropylene wood-plastic composite material and preparation method and application thereof |
| CN112519287A (en) * | 2020-10-22 | 2021-03-19 | 广西特斯途汽车科技有限公司 | Anti-exposure and anti-aging automobile charging pile shell |
| EP4206236A1 (en) * | 2021-12-28 | 2023-07-05 | Kao Corporation | Compounds, their synthesis and compositions comprising the compounds for enhanced deposition of polymers onto hair surfaces |
| CN117362755A (en) * | 2023-10-12 | 2024-01-09 | 广州工程技术职业学院 | Modified filler, polypropylene composite material for 3D printing and preparation method of polypropylene composite material |
| CN117362755B (en) * | 2023-10-12 | 2024-08-13 | 广州工程技术职业学院 | Modified filler, polypropylene composite material for 3D printing and preparation method of polypropylene composite material |
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