CN111848867A - Digital light processing 3D printing palm oil-based thermoplastic elastomer - Google Patents
Digital light processing 3D printing palm oil-based thermoplastic elastomer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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Abstract
The invention belongs to the technical field of high polymer elastomer materials, and particularly relates to a digital light processing 3D printing palm oil-based thermoplastic elastomer and a preparation method thereof. The method comprises the steps of taking biomass resource palm oil as a raw material, synthesizing palm oil fatty acid acrylamide ethyl ester, blending the palm oil fatty acid acrylamide ethyl ester with acrylic acid, and preparing the environment-friendly palm oil-based thermoplastic elastomer by a digital light processing 3D printing technology under the action of a photoinitiator. The palm oil-based thermoplastic elastomer prepared by the invention is environment-friendly, and has good tensile strength and tensile elongation at break.
Description
Technical Field
The invention belongs to the technical field of high polymer elastomer materials, and particularly relates to a digital light processing 3D printing palm oil-based thermoplastic elastomer and a preparation method thereof.
Background
Elastomers are widely used in industrial and medical applications. However, bio-based elastomers face many challenges, including high cost and low performance, which greatly limit their competitiveness in the market place. The problem of high cost can be solved by using abundant and cheap biomass resources. In recent years, due to the high importance of renewable resources, many bio-based elastomers have been developed for manufacturing and applications. For example, the global yield of vegetable oils is close to 2 million tons, a renewable resource with promising application prospect, and can be used for producing low-cost and high-value bio-based elastomers. Palm oil is the largest vegetable oil produced, consumed and traded worldwide. Therefore, the palm oil has the characteristics of reproducibility, richness, low cost, intensive growth and the like, and has good commercial utilization prospect. The basic structure of vegetable oils is triglycerides, and elastomers prepared based thereon contain more flexible chains and cross-linked structures, resulting in poor mechanical properties, i.e. low elongation, low strength and modulus, for many elastomers.
On the other hand, 3D printing is a viable method to simplify the process flow. Among various manufacturing techniques, 3D printing is distinguished by its infinite pattern, simplicity of operation, and the like. Therefore, the 3D printing technology has wide application prospect in the engineering fields of medical instruments, aerospace structures, energy equipment, soft robots and the like. However, the ultimate potential of 3D printing is limited by a number of factors, with printing speed and versatility of materials being the most critical. From a printing speed perspective, Digital Light Processing (DLP) has significant advantages over other processes such as fused deposition techniques (FDM) and stereolithography techniques (SLA). The "inks" used in DLP technology are photo-initiated free radical polymerizable acrylic/methacrylic systems and photo-initiated cationic polymerizable epoxy resins. These resins, upon photo-initiated polymerization, can form three-dimensionally crosslinked thermoset polymers in the unpolymerized liquid resin, thereby achieving the separation of the 3D printed object from the liquid "ink". Therefore, rapid solid-liquid separation is critical to DLP printing technology and is currently limited to the use of thermosetting resins. Although there are many photo-polymerizable thermoplastic resins, most of them are easily dissolved in an unpolymerized monomer solution and cannot achieve a rapid solid-liquid separation effect. Thermoplastic polymers require two conditions to be met using photocuring printing techniques: firstly, the polymerization rate of the monomer is high, namely the speed of the formed polymer dissolved in the monomer solution is higher; secondly, the glass transition temperature of the polymer should be higher than the printing temperature, because if the polymer is in a glass state, the molecular chain moving capability of the polymer is strong, and the dissolution of the polymer is accelerated. In fact, the solubility of a polymer is also related to factors such as crystallinity, molecular weight, flexibility, intermolecular forces, and the like. Based on this, the present project proposes the assumption that: if the molecular weight of the polymer is large enough and a certain interaction force exists between molecular chains, such as strong hydrogen bonding, the polymer is difficult to dissolve in a monomer solution and can be prepared by adopting a photocuring printing technology.
The biomass palm oil is used as a raw material to synthesize a palm oil propenyl monomer capable of photo-initiated polymerization, and the palm oil propenyl monomer is copolymerized with acrylic acid, so that hydrogen bond combination is constructed in the elastomer, the difficulty of solid-liquid separation during photo-curing printing of thermoplastic materials is solved, the preparation method of the biomass elastomer is provided, efficient utilization of palm oil resources and research and development of new products are developed, the use of petroleum-based products can be reduced, and the development of low-carbon economy is facilitated.
Disclosure of Invention
The invention aims to provide a digital light processing 3D printing palm oil-based thermoplastic elastomer and a preparation method thereof aiming at the defects of the prior art, and solves the problems that the mechanical property of a vegetable oil elastomer is poor, the preparation process is complex, the photocuring printing of a thermoplastic material is difficult to separate solid from liquid, and the like; the prepared palm oil-based thermoplastic elastomer is environment-friendly and has good tensile strength and tensile elongation at break.
In order to achieve the purpose, the invention adopts the following technical scheme:
the raw material composition of the digital light processing 3D printing palm oil-based thermoplastic elastomer comprises the following components in parts by mass: 10-50 parts of Acrylic Acid (AA), 50-90 parts of palm oil allyl monomer and 1-2 parts of photoinitiator.
The Palm oil allyl monomer is Palm oil fatty acid acrylamide ethyl ester (POFA-EA).
The molecular structural formula of the palm oil fatty acid acrylamide ethyl ester is as follows:
The photoinitiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The palm oil fatty acid acrylamide ethyl ester is synthesized from environment-friendly and green raw materials, and the synthesis process comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedN-hydroxyethyl acrylamide, 0.1g 2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The specific preparation steps of the digital light processing 3D printing palm oil-based thermoplastic elastomer are as follows: uniformly mixing AA, POFA-EA and a photoinitiator, pouring the mixture into a digital light processing 3D printer, and printing at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
The invention has the beneficial effects that:
1) the digital light processing 3D printing palm oil-based thermoplastic elastomer prepared by the invention is a thermoplastic elastomer with high bio-based content, no toxic solvent and environmental friendliness; the elastomer has good tensile strength and tensile elongation at break. Meanwhile, the green and harmless palm oil with low price and high yield is used as the raw material, and a new method for utilizing the palm oil is developed.
2) According to the invention, an optimized process parameter combination is adopted, the use amount ratio (mass ratio) of acrylic acid to the palm oil allyl monomer is 4:6, the use amount of the photoinitiator is 2wt%, the ultraviolet wavelength of a digital light processing 3D printer is 405nm, the printing speed is 20mm/h, and the palm oil-based thermoplastic elastomer with excellent mechanical properties can be prepared.
Drawings
FIG. 1 is a reaction synthesis mechanism diagram of palm oil fatty acid acrylamide ethyl ester.
FIG. 2 shows nuclear magnetic resonance (a) hydrogen spectrum of ethyl acrylamide palmitate (A)1H NMR and (b) a carbon spectrum of (A), (B)13CNMR）。
FIG. 3 is a tensile stress-strain curve of a palm oil-based thermoplastic elastomer; wherein P9A1 represents an elastomer copolymerized with 90wt% POFA-EA and 10wt% AA; P8A2 represents an elastomer copolymerized with 80wt% POFA-EA and 20wt% AA; P7A3 represents an elastomer copolymerized with 70% by weight POFA-EA and 30% by weight AA; P6A4 represents an elastomer copolymerized with 60% by weight POFA-EA and 40% by weight AA; P5A5 represents an elastomer copolymerized with 50wt% POFA-EA and 50wt% AA, the same applies below.
Fig. 4 is the tensile elongation at break and the breaking strength of the palm oil-based thermoplastic elastomer.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Raw materials: palm Oil (PO) (melting point: 18 °)C; acid value: 0.16mg KOH/g) was purchased from Shanghai Dingfen chemical technology, Inc., China; acrylic Acid (AA),N- (2-hydroxyethyl) acrylamide, 2, 6-dimethylphenol, and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, available from Shanghai pure (Aladdin) industries, Inc.; sodium chloride, dichloromethane, zinc oxide, sodium hydroxide and tetrahydrofuran were purchased from Shanghai pharmaceutical group chemical Co., Ltd.
The reaction mechanism of the synthesis process is shown in figure 1.
Nuclear magnetic resonance (a) hydrogen spectrum of the product of palm oil fatty acid acrylamide ethyl ester (a)1H NMR and (b) a carbon spectrum of (A), (B)13CNMR) is shown in fig. 2.
Example 1
Digital light processing 3D printing of palm oil-based thermoplastic elastomer:
the synthesis process of palm oil fatty acid acrylamide ethyl ester comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedN-hydroxyethyl acrylamide, 0.1g 2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The preparation method of the elastomer comprises the following steps: 18g of palm oil propenyl monomer, 2g of acrylic acid and 0.4g of photoinitiator are mixed uniformly and poured into a digital light processing 3D printer, and printing is carried out at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
In the preparation process, the dosage ratio of the palm oil allyl monomer to the acrylic acid is 9:1 in mass ratio; the amount of initiator used was 2% by mass of the elastomer.
Example 2
Digital light processing 3D printing of palm oil-based thermoplastic elastomer:
the synthesis process of palm oil fatty acid acrylamide ethyl ester comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedNHydroxyethyl acrylamide, 0.1g of 2, 6-dimethylphenol,5g of sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The preparation method of the elastomer comprises the following steps: 16g of palm oil propenyl monomer, 4g of acrylic acid and 0.4g of photoinitiator are mixed uniformly and poured into a digital light processing 3D printer, and printing is carried out at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
In the preparation process, the dosage ratio of the palm oil allyl monomer to the acrylic acid is 8:2 in terms of mass ratio; the amount of initiator used was 2% by mass of the elastomer.
Example 3
Digital light processing 3D printing of palm oil-based thermoplastic elastomer:
the synthesis process of palm oil fatty acid acrylamide ethyl ester comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedN-hydroxyethyl acrylamide, 0.1g 2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The preparation method of the elastomer comprises the following steps: 14g of palm oil propenyl monomer, 6g of acrylic acid and 0.4g of photoinitiator are mixed uniformly and poured into a digital light processing 3D printer, and printing is carried out at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
In the preparation process, the dosage ratio of the palm oil allyl monomer to the acrylic acid is 7:3 in mass ratio; the amount of initiator used was 2% by mass of the elastomer.
Example 4
Digital light processing 3D printing of palm oil-based thermoplastic elastomer:
the synthesis process of palm oil fatty acid acrylamide ethyl ester comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedNHydroxyethyl acrylamide, 0.1g2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The preparation method of the elastomer comprises the following steps: uniformly mixing 12g of palm oil propenyl monomer, 8g of acrylic acid and 0.4g of photoinitiator, pouring the mixture into a digital light processing 3D printer, and printing at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
In the preparation process, the dosage ratio of the palm oil allyl monomer to the acrylic acid is 6:4 in mass ratio; the amount of initiator used was 2% by mass of the elastomer.
Example 5
Digital light processing 3D printing of palm oil-based thermoplastic elastomer:
the synthesis process of palm oil fatty acid acrylamide ethyl ester comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedN-hydroxyethyl acrylamide, 0.1g 2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
The preparation method of the elastomer comprises the following steps: 10g of palm oil propenyl monomer, 10g of acrylic acid and 0.4g of photoinitiator are mixed uniformly and poured into a digital light processing 3D printer, and printing is carried out at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set program.
In the preparation process, the dosage ratio of the palm oil allyl monomer to the acrylic acid is 5:5 in terms of mass ratio; the amount of initiator used was 2% by mass of the elastomer.
Testing the mechanical property of the elastomer:
the elastomer was made into a dumbbell-shaped specimen (specification: length 80mm, width at both ends 10mm, width at the middle 5mm, thickness 1.5 mm) to test tensile properties; the tensile property test is carried out according to the GB1447-05 standard. The tensile property test is completed on a microcomputer controlled electronic universal tester.
Tensile properties of palm oil-based resin elastomer:
as can be seen from FIGS. 3 and 4, the tensile stress of the palm oil-based elastomers copolymerized with POFA-EA and AA increased with increasing amounts of AA, and the stresses of the elastomers P9A1, P8A2, P7A3, P6A4 and P5A5 were 0.23MPa, 0.31MPa, 0.58MPa, 0.74MPa and 0.87MPa, respectively. While the tensile strain peaked at P7a4 and subsequently subsided. The strains of elastomers P9a1, P8a2, P7A3, P6a4, and P5a5 were 315%, 449%, 649%, 557%, and 387%, respectively.
As can be seen from FIGS. 3 and 4, the breaking strength of the palm oil-based elastomers copolymerized with POFA-EA and AA increased with increasing amounts of AA, and the breaking strength of the elastomers P9A1, P8A2, P7A3, P6A4 and P5A5 were 0.24MPa, 0.34MPa, 0.59MPa, 0.76MPa and 0.87MPa, respectively. Whereas the elongation at break peaks at P7a4 and subsequently decreases. The elongations at break of the elastomers P9a1, P8a2, P7A3, P6a4 and P5a5 were 317%, 442%, 644%, 560% and 386%, respectively.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A digital light processing 3D prints palm oil base thermoplastic elastomer which characterized in that: the elastomer comprises the following raw materials in parts by weight: 10-50 parts of acrylic acid, 50-90 parts of palm oil allyl monomers and 1-2 parts of photoinitiator.
2. The digital light processing 3D printed palm oil-based thermoplastic elastomer of claim 1, wherein: the palm oil allyl monomer is palm oil fatty acid acrylamide ethyl ester; the structural formula is as follows:
3. The digital light processing 3D printed palm oil based high performance elastomer of claim 1, wherein: the palm oil fatty acid acrylamide ethyl ester is synthesized from environment-friendly and green raw materials, and the synthesis process comprises the following steps: placing 150g of palm oil and 150mL of tetrahydrofuran in a three-neck flask; 115g of this are subsequently addedN-hydroxyethyl acrylamide, 0.1g 2,6 dimethylphenol, 5g sodium hydroxide; then, placing the flask in a water bath kettle, magnetically stirring for 150 r/min, and reacting for 16h at 40 ℃; and (3) repeatedly purifying the reaction products by saturated salt water for 3-5 times, and then purifying by rotary evaporation to obtain the palm oil fatty acid acrylamide ethyl ester.
4. The digital light processing 3D printed palm oil-based thermoplastic elastomer of claim 1, wherein: the photoinitiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
5. A method of preparing the digital light processing 3D printed palm oil-based thermoplastic elastomer as claimed in any one of claims 1 to 4, wherein: the method comprises the following specific steps: acrylic acid, a palm oil propenyl monomer and a photoinitiator are mixed uniformly and poured into a digital light processing 3D printer, and printing is carried out at the speed of 20mm/h under the irradiation of ultraviolet light with the wavelength of 405nm according to a set printing model, so as to obtain the elastomer.
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