CN111053951A - Elastic degradable 3D printing porous scaffold and preparation method thereof - Google Patents
Elastic degradable 3D printing porous scaffold and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- 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
- B33Y10/00—Processes of additive manufacturing
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- 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
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- 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
- B33Y80/00—Products made by additive manufacturing
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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
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- 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
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
Abstract
The invention relates to the field of biological high polymer materials, in particular to an elastic degradable 3D printing porous scaffold and a preparation method thereof. In order to solve the problems that an acrylate end group is introduced into a cyclic acetal group degradable biological material, unreacted acrylate groups are easy to carry out Michael addition reaction with amino groups and sulfydryl groups on proteins in vivo, so that stimulation and toxicity to surrounding tissues are caused, and meanwhile, cross-linked acrylate groups are still likely to be degraded in vivo to generate acid groups, so that local acid environments stimulate the surrounding tissues and the hydrolysis of the material is accelerated, the invention provides an elastic degradable 3D printing porous scaffold.
Description
Technical Field
The invention relates to the field of biological high polymer materials, in particular to an elastic degradable 3D printing porous scaffold and a preparation method thereof.
Background
Articular cartilage of the human body is one of the most vulnerable tissues. Articular cartilage damage due to arthritis or athletic trauma is painful for many patients. The reason for this is that there is no blood vessel in the cartilage tissue, it is difficult to repair and heal spontaneously once damaged, and it is easy to induce more severe articular cartilage tissue damage. There are many kinds of repairing and treating methods for cartilage defect clinically, including the application of autologous tissue, allograft, prosthesis material or the compound application of the above methods. However, autologous bone is available in limited sources, while xenogenic bone is antigenic, and fails to implant due to severe immune rejection, and also risks of contracting the disease. The wide use of various bone substitute materials is also always unsatisfactory in biological and mechanical function. If the diseased or damaged bone tissues can be restored to the natural state, the bone defect repair is extremely achieved, and the emerging tissue engineering is helpful for solving the problems.
The tissue engineering is to plant the normal tissue cells cultured and expanded in vitro onto porous rack with good biocompatibility and gradually degradable absorption in vivo to form cell rack compound, proliferate and differentiate the cells on the rack, implant the compound into the damaged part of organism tissue, continue to proliferate and secrete extracellular matrix in vivo, and form new tissue or organ adaptive to self function and form with the gradual degradation of rack material, so as to repair the damaged tissue or organ. The three-dimensional scaffold for cartilage tissue engineering is a microenvironment for growth of cartilage cells, not only provides a framework for growth attachment of cartilage cells to form specific tissues or organs, but also plays a role in mediating signal transmission and interaction among cells as one of extracellular matrix components. Thus, its properties have a significant influence on the growth of chondrocytes. In addition, cartilage in a human body has very special mechanical properties, such as articular cartilage, has good elasticity and toughness, can bear larger load, has a smooth surface and ensures that the friction force during joint movement is very small, but the cartilage tissue engineering can not reproduce cartilage tissue with the same mechanical properties as the natural cartilage, which is the biggest problem faced by the current cartilage tissue engineering. Therefore, the material design, the scaffold forming method and the special mechanical properties of the scaffold material play a key role in the construction of the cartilage tissue engineering scaffold.
The biodegradable Materials for cartilage tissue Engineering scaffolds are currently divided into natural polymer Materials and synthetic polymer Materials, degradable synthetic biopolymers are widely studied as tissue Engineering scaffold Materials, such Materials generally have good mechanical properties, are easy to control through chemical or physical modification, have certain bioactivity, and are easy to process into scaffolds with specific porous morphology and structure to support tissue growth, synthetic Materials mainly include polyglycolic acid, polylactide PLA, and copolymers PLGA and the like (forest water, poplar, Dacron. tissue Engineering meniscus research and development [ J ] Chinese clinical rehabilitation, 2004 (5)) which have good mechanical properties and degradation speed controllability, however, they are hydrophobic Materials and have poor biocompatibility, and in addition, the degradation products thereof are acidic, so that the pH value of surrounding tissues of the implanted Materials is reduced, severe inflammatory reactions are easily caused, recently, degradable biological Materials based on acetal, cyclic acetal and ketal units as non-acidic substances cause more and more attention, especially, the degradation of cyclic acetal-based biological Materials containing cyclic acetal groups are more and more easily caused by hydrolysis reaction of the polyethylene glycol-carbonyl acrylate-terminated polymers and the polyethylene glycol-carbonyl acrylate-terminated polymers to generate a mild degradation reaction in tissues and the environment when the hydrolysis reaction of the biodegradable Materials is carried out in vivo, and the hydrolysis reaction of the biological tissue (hydrolysis reaction of polyethylene glycol-carbonyl acrylate-degrading biological tissue, the biological hydrogel-degrading biological tissue, such as a hydrogel-degrading hydrogel-2-degrading hydrogel-2-degrading hydrogel-a biological material, a biological tissue-degrading hydrogel-E-degrading biological tissue-E-a biological tissue with a biological tissue-degrading biological tissue.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the problems that an acrylate end group is introduced into a cyclic acetal group degradable biological material, unreacted acrylate group is easy to carry out Michael addition reaction with amino and sulfydryl on protein in vivo so as to cause stimulation and toxicity to surrounding tissues, and simultaneously cross-linked acrylate groups are still likely to degrade in vivo to generate acid groups so as to cause local acid environment to stimulate the surrounding tissues and accelerate the hydrolysis of the material, the invention provides an elastic degradable 3D printing porous scaffold, which is formed by crosslinking and photocuring a cyclic acetal polymerized monomer I, a cyclic acetal polymerized monomer II and polyethylene glycol allyl carbonate (PEGDAC) as polymerized monomers and a cross-linking agent containing sulfydryl, and has better rebound resilience and can better cope with the extrusion of the porous scaffold caused by human activities in the cartilage tissue repair process, the porous bracket is always kept in the original designed shape, and is beneficial to better repair the cartilage tissue of the human body.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides an elastic degradable 3D printing porous scaffold which comprises the following components in parts by weight:
100 portions of main resin
0.1 to 0.5 portion of photoinitiator
0.01-0.05 part of light absorber
The main resin comprises the following components in parts by weight:
100 portions of cyclic acetal polymerized monomer
50-200 parts of PEGDAC
The main resin also comprises a crosslinking agent containing sulfydryl, and the molar ratio of the sulfydryl in the crosslinking agent containing sulfydryl to double bonds in the cyclic acetal polymerized monomer is 1:1.
The cyclic acetal polymerized monomer comprises the following components in parts by weight:
1-100 parts of cyclic acetal polymerized monomer
10 parts of cyclic acetal polymerized monomer II.
Specifically, the molecular structure of the cyclic acetal polymerized monomer I is as follows:
specifically, the molecular structure of the cyclic acetal polymeric monomer II is as follows:
specifically, the molecular structure of the PEGDAC is as follows:
wherein n is 1-15.
Specifically, the synthesis method of the PEGDAC comprises the following steps:
dissolving 0.04mol of polyethylene glycol containing hydroxyl in 25mL of CH2Cl2Adding 0.2g of catalyst 4-dimethylaminopyridine and 6.00g of triethylamine, stirring for 30min to mix uniformly,then placed in an ice bath and dropwise added with 7.20g of allyl chloroformate and 25mL CH2Cl2The mixture is dripped in 4 hours, stirred and reacted for 48 hours, and after the reaction is finished, salt is removed by suction filtration and CH is used2Cl2Washing the salt three times to obtain an organic phase, and respectively using 1mol/L hydrochloric acid solution and saturated NaHCO to the organic phase3The solution, deionized water and saturated NaCl solution were washed three times each, and the solvent was removed by distillation under reduced pressure to obtain a transparent liquid of PEGDAC.
Specifically, the synthesis method of the cyclic acetal polymeric monomer II is as follows:
dissolving 5.9g of trimethylolpropane and 3.0g of 2, 2-dimethyl-3-hydroxypropionaldehyde in 20mL of 1mol/L hydrochloric acid solution, heating to 90 ℃, stirring and reacting for 24 hours under the nitrogen atmosphere, extracting the mixed solution by using trichloromethane after the reaction is finished, respectively washing the extract liquid by using deionized water and saturated sodium chloride for three times, and removing the solvent by reduced pressure distillation after the washing is finished to obtain a white solid product, namely, a cyclic acetal polymerized monomer II.
Specifically, the molar ratio of the mercapto group in the mercapto group-containing crosslinking agent to the double bond in the cyclic acetal polymerized monomer is 1:1.
Specifically, the thiol-group-containing crosslinking agent is a thiol-group-containing 3-functionality or 4-functionality crosslinking agent.
Specifically, the crosslinking agent containing sulfydryl is TTMP or PETMP.
Specifically, the photoinitiator was 784 or a mixture of CQ (camphorquinone) and EDMAB (ethyl 4-N, N-dimethylaminobenzoate) wherein the mass ratio of CQ to EDMAB was 1:1.
An elastic degradable 3D printing porous scaffold is prepared according to the following steps:
mixing cyclic acetal polymerized monomers, PEGDAC and a cross-linking agent uniformly, then adding a photoinitiator and a light absorber, stirring uniformly at room temperature, and printing out the elastic degradable 3D printing porous scaffold by a DLP3D printer.
The invention has the beneficial effects that:
(1) the elastic degradable 3D printing porous scaffold prepared by crosslinking photocuring 3D printing with two cyclic acetal group polymerizable monomers taking vinyl carbonate as end groups, PEGDAC and a crosslinking agent completely does not contain acidic substances in degradation products, does not have the phenomenon of self-accelerated degradation, and has small irritation of the degradation products to surrounding tissues of an installation position;
(2) the elastic degradable 3D printing porous scaffold prepared by adjusting the proportion of the two cyclic acetal group polymerization monomers and the soft segment content of the PEGDAC has high resilience.
Drawings
FIG. 1: is an infrared spectrum of PEGDAC (n ═ 15).
FIG. 2: is an infrared spectrum of the cyclic acetal polymerized monomer II.
FIG. 3: is a cyclic acetal monomer II1HNMR spectrogram.
Detailed Description
The present invention will now be described in further detail with reference to examples.
(1) The preparation examples of PEGDAC include but are not limited to the following steps:
dissolving 0.04mol of polyethylene glycol containing hydroxyl in 25mLCH2Cl2Adding 0.2g of catalyst 4-dimethylaminopyridine and 6.00g of acid-binding agent triethylamine, stirring for 30min to mix uniformly, then placing in an ice bath, and dropwise adding 7.20g of allyl chloroformate and 25mL of CH2Cl2The mixture is dripped over 4 hours, stirred and reacted for 48 hours after the dripping is finished, the salt is removed by suction filtration after the reaction is finished, and CH is used2Cl2Washing the salt three times to obtain an organic phase, and respectively using 1mol/L hydrochloric acid solution and saturated NaHCO to the organic phase3The solution, deionized water and saturated NaCl solution were washed three times each, and the solvent was removed by distillation under reduced pressure to obtain a transparent liquid of PEGDAC. Fig. 1 shows an infrared spectrum of PEGDAC (n ═ 15), from which it was found that the stretching vibration peak of — OH disappeared, and thus, this method was successful in producing PEGDAC (n ═ 15).
(2) The preparation examples of the cyclic acetal polymerized monomer II, but not limited to, are as follows:
dissolving 5.9g of trimethylolpropane and 3.0g of 2, 2-dimethyl-3-hydroxypropionaldehyde in 20mL of 1mol/L hydrochloric acid solution, heating to 90 ℃, and stirring and reacting under nitrogen atmosphereReacting for 24h, extracting the mixed solution with chloroform, washing the extractive solution with deionized water and saturated sodium chloride for three times, distilling under reduced pressure to remove solvent to obtain white solid product cyclic acetal polymeric monomer II, the infrared spectrogram is shown in FIG. 2, wherein 3266cm is shown in the figure-1The peak is a stretching vibration absorption peak of-OH, 2966cm-1And 2861cm-1is-CH3，-CH21466cm in peak of absorption of stretching vibration-1Is of the formula-CH3，-CH2Bending vibration absorption peak of (1), 1048cm-1The peak is the stretching vibration absorption peak of-C-O-C. 1700cm are found in the infrared image-1The stretching vibration absorption peak of the left and right aldehyde characteristics disappears, which indicates that the aldol condensation reaction has occurred; process for preparing cyclic acetal monomers II1The NMR nuclear magnetic mass spectrum is shown in FIG. 3, in which a is. delta.0.83 (3H, CH)3CH2-, b is delta 0.94(6H, -C (CH)3)2CH2-, c is. delta.1.20 (2H, CH)3CH2-, d is delta 3.40-3.50(4H, -C (CH)3)2CHOH,-CCH2OH), e is delta 3.86(2H, -CCH2OH), f is delta 3.97(2H, -CCH2O-), and g is delta 4.26(1H, -OCHO-), from which it can be seen that this process has succeeded in preparing the cyclic acetal polymeric monomer II.
(3) The preparation method of the elastic degradable 3D printing porous scaffold comprises the following steps:
uniformly mixing a cyclic acetal polymerized monomer, PEGDAC and a cross-linking agent, wherein the molar ratio of sulfydryl in the cross-linking agent to double bonds in the cyclic acetal polymerized monomer is 1:1, then adding a photoinitiator and a light absorber, uniformly stirring at room temperature, and printing the elastic degradable 3D printing porous scaffold by a DLP3D printer.
Examples 1-3 and comparative examples 1-4 elastic degradable 3D printed porous scaffolds were prepared according to the above procedure, the composition of which is shown in table 1 below:
TABLE 1
Comparative example 5 differs from example 1 in that: the crosslinker used was 1, 6-hexanedithiol.
Comparative example 6 differs from example 1 in that: the molar ratio of mercapto group in the crosslinking agent to double bond in the cyclic acetal polymerized monomer is 1: 1.1.
And (3) performance testing:
1. the performance tests of the elastically degradable 3D printed porous scaffolds prepared in examples 1-3 and comparative examples 1-6 are shown in table 2:
TABLE 2
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An elastic degradable 3D printing porous scaffold is characterized by comprising the following components in parts by weight:
100 portions of main resin
0.1 to 0.5 portion of photoinitiator
0.01 to 0.05 portion of light absorbent,
the main resin comprises the following components in parts by weight:
100 portions of cyclic acetal polymerized monomer
50-200 parts of PEGDAC
The main resin also comprises a crosslinking agent containing sulfydryl, and the molar ratio of the sulfydryl in the crosslinking agent containing sulfydryl to double bonds in the cyclic acetal polymerized monomer is 1:1.
2. The elastically degradable 3D printed porous scaffold of claim 1, wherein: the cyclic acetal polymerized monomer comprises the following components in parts by weight:
1-100 parts of cyclic acetal polymerized monomer
10 parts of cyclic acetal polymerized monomer II.
3. The elastically degradable 3D printed porous scaffold of claim 2, wherein: the molecular structure of the cyclic acetal polymerized monomer I is as follows:
4. the elastically degradable 3D printed porous scaffold of claim 2, wherein: the molecular structure of the cyclic acetal polymerized monomer II is as follows:
5. the elastically degradable 3D printed porous scaffold of claim 1, wherein: the molecular structure of the PEGDAC is as follows:
wherein n is 1-15.
6. The elastically degradable 3D printed porous scaffold of claim 1, wherein: the thiol-group-containing cross-linking agent is a thiol-group-containing 3-functionality or 4-functionality cross-linking agent.
7. The elastically degradable 3D printed porous scaffold of claim 6, wherein: the crosslinking agent containing sulfydryl is TTMP or PETMP.
8. The elastically degradable 3D printed porous scaffold of claim 1, wherein: the photoinitiator was 784 or a mixture of CQ and photoinitiator EDMAB, wherein the mass ratio of CQ to EDMAB was 1:1.
9. The elastically degradable 3D printed porous scaffold of claim 1, wherein: the light absorbent is carotene.
10. An elastic degradable 3D printing porous scaffold is characterized by being prepared according to the following steps:
mixing cyclic acetal polymerized monomers, PEGDAC and a cross-linking agent uniformly, then adding a photoinitiator and a light absorber, stirring uniformly at room temperature, and printing out the elastic degradable 3D printing porous scaffold by a DLP3D printer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516932A (en) * | 2020-11-19 | 2022-05-20 | 中国科学院福建物质结构研究所 | Bio-based transparent degradable flexible resin and preparation method thereof |
| CN114656590A (en) * | 2020-12-07 | 2022-06-24 | 中国科学院福建物质结构研究所 | Degradable thermosetting 3D printing mold and preparation method thereof |
| CN115873174A (en) * | 2022-11-22 | 2023-03-31 | 明澈生物科技(苏州)有限公司 | Two-photon 3D printing photosensitive composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070059337A1 (en) * | 2005-08-31 | 2007-03-15 | Fisher John P | Cyclic acetal biomaterials |
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- 2019-12-31 CN CN201911422905.7A patent/CN111053951A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070059337A1 (en) * | 2005-08-31 | 2007-03-15 | Fisher John P | Cyclic acetal biomaterials |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516932A (en) * | 2020-11-19 | 2022-05-20 | 中国科学院福建物质结构研究所 | Bio-based transparent degradable flexible resin and preparation method thereof |
| CN114516932B (en) * | 2020-11-19 | 2022-12-02 | 中国科学院福建物质结构研究所 | Bio-based transparent degradable flexible resin and preparation method thereof |
| CN114656590A (en) * | 2020-12-07 | 2022-06-24 | 中国科学院福建物质结构研究所 | Degradable thermosetting 3D printing mold and preparation method thereof |
| CN115873174A (en) * | 2022-11-22 | 2023-03-31 | 明澈生物科技(苏州)有限公司 | Two-photon 3D printing photosensitive composition |
| CN115873174B (en) * | 2022-11-22 | 2023-11-10 | 明澈生物科技(苏州)有限公司 | Two-photon 3D printing photosensitive composition |
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