CN108079377A - A kind of polyglycolic acid resin composite material and its manufacturing method - Google Patents
A kind of polyglycolic acid resin composite material and its manufacturing method Download PDFInfo
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- CN108079377A CN108079377A CN201711338935.0A CN201711338935A CN108079377A CN 108079377 A CN108079377 A CN 108079377A CN 201711338935 A CN201711338935 A CN 201711338935A CN 108079377 A CN108079377 A CN 108079377A
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- polyglycolic acid
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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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
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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
- A61L27/58—Materials at least partially resorbable by the body
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/128—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing other specific inorganic fillers not covered by A61L31/126 or A61L31/127
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Surgery (AREA)
- Heart & Thoracic Surgery (AREA)
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- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention provides a kind of polyglycolic acid resin composite material and its manufacturing method, contain 30~40%wt polyglycolic acid resins, 20~30%wt inorganic filling materials and 30~50% reinforcing material in the polyglycolic acid composite material, after being surface-treated to inorganic filling material and reinforcing fiber, in double screw extruder after honey refining, the extrusion die extrusion molding of extruded machine.Due in polyglycolic acid composite material, in addition to inorganic filling material, remaining is the biocompatible material compatible with animal or human body, therefore the composite material can be also used as packaging material and the material of drilling well downhole tool and component and use as animal or the supporting material of skeleton and fracture fixation material.
Description
Technical field
The invention belongs to high molecular material manufacturing field, it be related to polyglycolic acid resin biological degradability and into
It is had excellent performance in terms of type, mechanical property, also existing has good heat resistance and water-disintegrable polyglycolic acid resin composite wood
Material and its manufacturing method.
Background technology
High molecular material it is just increasingly extensive be applied to medical domain.In the research and development of medical macromolecular materials,
Degradable high polymer material is in operation suture thread, artificial skin, artificial blood vessel, bone fixation and reparation, drug controlled release
And many fields such as red blood cell carrier are applied, many developed countries proceed by from nineteen sixties grinds
Study carefully, initial degradable material is only applied to medicament slow release, suture etc., to the 1980s with high molecular polymerization skill
The development of the development of art and plastic processing technology, especially fiber reinforcement technology, degradable bone material just have larger development sky
Between.
Recognized by domestic and international extensive investigations research, clinically due to wound etc. cause the incidence of bone defect compared with
Height, existing method is always to use internal fixation material of the stainless steel and other metal materials as repairing bone, but it has it significantly
Shortcoming:First, due to the firm stimulation that can reduce section physiological stress of metal material, forming function replacement, both stress shielding is protected
Shield, so as to form osteoporosis；Second is that due to metal material cannot biodegradation needed after knitting second of operation take out,
Add the pain of patient；Third, metal, which fixes material, can cause some complication.More than reason is based on, it is desirable to find one
It kind can meet the fixed needs of repairing bone and biodegradable material substitutes widely used stainless steel material in vivo
As repairing bone internal fixation material.There are many biodegradable polymer at present, but common are and be possibly used for bone peak and apply for another
The synthesized degradable high molecular material in domain only has polyethanol acids and polyacids esters.Wherein polyethanol acrylic materials are led in Orthopeadic Surgery
Application in domain has remarkable progress from laboratory to clinic.Polyethanol acrylic materials are at present still in the development stage.Bone is used can
Degradable material from now on further research be concentrated mainly on the intensity for improving polymer and the composition of further investigated polymer, structure with
The relations such as physical mechanical property, biodegradability and solve the problems, such as complication etc. after implantation.
As medical material, it is the most important condition to have good biocompatibility, while also needs to certain mechanicalness
Energy and hot property etc..Long-term external, experiment in vivo are had to pass through based on these condition biodegradable polymers to investigate
Afterwards, medical domain can be applied to.The degradation of high molecular material considers that there are homogeneous and heterogeneous two kinds of degradations from physics aspect
Mechanism.It when degradation reaction occurs over just polymer surfaces, degrades to be heterogeneous and (is also known as superficial degradation), and homogeneously degrade then
It is that degradation reaction occurs in entire high molecular material.Chemically angle considers that there are following threes for the degradation of high molecular material
Mechanism:
Hydrophobic polymer material becomes low molecular weight, water soluble molecules by unstable strong hydrolysis on main chain.
High molecular material not soluble in water is hydrolyzed by side-chain radical, the ionization or protonation of side group, is degraded into water-soluble
Property small molecule.Crosslinking chain high molecular material not soluble in water, first hydrolysis fall unstable cross linked chain and become can be in water
Then linear polymeric is degraded into small-molecule substance in the solution.
Some common medical biodegradable polymeric degradation mechanisms and its structural relation, show high molecular material
Degradation is usually to become the process of soluble small molecule after unstable weak bond destroys.
It is just increasing in the Biodegradable Polymers for Medical Applications applied or studied at present, it can by its source
It is divided into chemical synthesis macromolecule, biotechnology synthesis macromolecule and natural polymer.What application was wider at present is synthesis macromolecule,
Especially polyethanol acids synthesis macromolecule just has attracted increasing attention, and has boundless prospects.
Aliphatic poly ethyl alcohol acrylic materials are most studies, most widely used synthesis high molecular material, especially polyethanol
Acid, polylactic acid, polycaprolactone and its copolymer.Substantial amounts of research shows that aliphatic poly ethyl alcohol acrylic materials have good life
Object degradability and biocompatibility.
Polyglycolic acid（Also known as polyglycolic acid or polyglycolide are most simple in polyhydroxyalkanoate
Linear polyglycolic acid, chemical constitution is as follows：The initial raw material of polyglycolic acid is
Glycolic is widely present in nature, especially in sugarcane, beet and immature grape juice.Because its separating-purifying difficulty is big,
It is industrial at present be all by the method for organic synthesis obtain to.Polyglycolic acid is the polymer of crystal type, crystallinity for 46~
52%, density is 1.5~1.64g/cm3, and glass transition temperature is 36 DEG C or so, and fusing point is about 224 DEG C, high-molecular-weight poly second
Alkyd good mechanical properties.Because polyglycolic acid is compact crystal polymer, in addition to hexafluoroisopropanol, it is practically insoluble in all
Organic solvent.Polyglycolic acid is a kind of thermoplastic linear polyglycolic acid, has certain processability, can use general equipment
Extrusion, injection, spinning, blowing.
Polyglycolic acid it from 'alpha '-hydroxy acids, i.e. glycolic.Glycolic is that normal human produces in metabolic processes
Raw, the polymer of glycolic is exactly polyglycolic acid (Polyglycolic acido, PGA).
Polyglycolic acid is a kind of synthesis high molecular material with good biodegradability properties and biocompatibility, and traditional
The high molecular material that performance is stablized, such as differences such as plastics, rubber, polyglycolic acid as material use after a certain period of time by
It gradually degrades, and ultimately becomes to human body, animals and plants and the harmless water and nitrogen of natural environment.The application of polyglycolic acid mainly shows
At biomedical and ecological two aspects.
The biomedical applications of polyglycolic acid be mainly manifested in suture, medicine controlled release carrier, fracture fixation material,
Tissue engineering bracket, suture supporting material.
Application of the polyglycolic acid on ecology is substituted in as the totally biodegradable plastics to environmental beneficial
The general-purpose plastics of widely applied Biostatic in plastics industry.Polyglycolic acid is mainly used as slow-releasing system, controls herbicide
Rate of release.Using polyglycolic acid plastic agricultural film most apparent advantage is that will not be as the polyethylene that largely uses at present and poly-
Vinyl chloride causes environmental pollution like that, and this film is automatically degradable after using several years, will not contaminated land and water source.Poly- second
Alkyd plastics also acts as forestry timber, aquatic products material and soil, the water-keeping material of desert afforestation.
Polyglycolic acid is tensile strength, extensibility, bends by force compared with the other biologicals Devlopment of Degradable Plastics such as polylactic acid
The very outstanding crystalline resin such as degree, crooked elastic rate, hardness, flexibility, heat resistance, belonging to possess can be equal to or surmount
The biodegradable plastic of the gas barrier property of general gas barrier resin.Polyglycolic acid can be shaped as using extrusion molding film or
Thin slice.
Polyglycolic acid resin, hereinafter referred to as " PGA " and polylactic resin, the hereinafter referred to as aliphatic polyesters such as " PLA "
Since the microorganism that can be present in the medium nature of soil and ocean or enzyme are decomposed, as one kind for environment
It bears smaller biodegradable polymer and gets most of the attention.In addition, aliphatic polyester in organism due to decomposing
Absorbability, therefore also utilized as the medical high molecular material such as surgical suture and artificial skin.
Even if among aliphatic polyester, PGA is with while outstanding mechanical strength is possessed, in resistance oxygen, barrier
It is also very excellent in the gas barrier properties such as carbon gas barrier property, barrier vapor and fragrant gas barrier property.PGA, can to possess very high fusing point
Carry out melt molding, therefore as being well suited for practical Biodegradable resin, it is intended to expansion it is independent or with other resinous woods
Material etc. carries out Composite and purposes.That is PGA is with for as utilization injection molding, extrusion molding, compression forming, blowing
The common resin molding methods such as shaping are configured to the moulding material of product, also food as easy oxidation deterioration etc.
Packaging material and easy compost, for the packaging material under environmental pressure, add, make full use of its intensity and degradation
Property, its decomposition etc. can be made by being positioned over after use in ground end, therefore also serve as forming oil or the pages such as production shale oil
The drilling well downhole tool of the natural gases such as rock gas or the material of its component and receive people expectation.
However, PGA is using water-disintegrable due to the root as biological degradability, and during melt-processed, molecular weight meeting
It reduces, further, it is difficult to be used for a long time under hot and humid environment.Also PGA is with because crystallization rate is comparatively fast being molded
Thick and solid ripple is generated on object；Or when the processing and forming of Composite is carried out with other thermoplastic resins, it is difficult to be prolonged
Type etc. is stretched into, problem occurs in processing and forming or product appearance.
In order to improve the heat resistance of Biodegradable resin, in Japan Patent number：Disclosed in special open JP2008-63577
A kind of Biodegradable resin formed by Biodegradable resin, thermoplasticity elastomer and inorganic filling material combines
Object, historically, the toughness and heat resistance of the Biodegradable resin composition are enhanced.As Biodegradable resin,
Polylactic acid (PLA), polyethylene succinate, polybutylene succinate, polybutylene succinate adipic acid, polyglycolic acid can be enumerated
(PGA) or poly-β-hybroxybutyric acid, poly- hydroxyl valerate, poly- hydroxycaproic ester, poly- beta-hydroxy heptanoate and poly- β-hydroxyl are contained
The polymer of the polyhydroxyalkanoatefrom of base butyrate-CO- hydroxyl valerates or polymer, the polypropylene of poly- hydroxy ester-ether
Carbonic ester, but the Biodegradable resin specifically used only has PLA, and the heat resistance of composition is to rest on 93.7 114 DEG C
Heat distortion temperature.
Therefore, it is necessary to such a PGA with composition：As the manufactured forming material using resins for universal use forming method
Material, in addition, making as food with the packaging material of other products and for the smaller packaging material of carrying capacity of environment even if also having
It can use to form the material of drilling well downhole tool or its component, with good mouldability, mechanical property
Meanwhile also have both outstanding heat resistance and water-disintegrable.
In Japanese Patent Laid-Open 10-60137, disclose and a kind of form polyglycolic acid using extrusion molding
The method of thin slice.The thickness of the thin slice is 0.01~5mm, and is flexibly manufactured with features such as obdurability, heat resistance, the transparencys
Various slice forming objects.
In Japanese Patent Laid-Open 2010-69718 publications, disclose and a kind of polyglycolic acid is subjected to curing extrusion molding
And the polyglycolic acid for making thickness or a diameter of 5~100mm cures extrusion molding object.Specifically, disclose by containing in temperature
Spend 270 DEG C and shear velocity 120sec 1In the case of the melt viscosity that measures be 10~1500Pa.s, particularly preferred 70~900
The resin material of the polyglycolic acid of Pa.s forms, possesses 1. 575 1. 625cm3Density and thickness or diameter exist
The polyglycolic acid of more than 5mm below 100mm cures extrusion molding object.
In Chinese patent number：Polyglycolic acid is described in CN201380047388.4 and cures extrusion molding object and its system
Method is made, wherein describing only the moulded parts of extrusion molding, and the fiber using macromolecule polyglycolic acid resin as raw material is manufactured
Technique is said nothing.
In Chinese patent number：A kind of polyglycolic acid composition and its manufacturer are described in CN201380047578.6
Method, wherein employing biocompatible material polylactic acid and silicon oxide-containing, silicate, carbonate, sulfate, clay mineral, inorganic
At least one of group of fibrous filler material and inorganic crystal whisker shape packing material；Due to polyglycolic acid and polylactic acid
It is biodegradation material, while is also influenced be subject to degradation time, therefore, which mends for animal or skeleton
During strong material, because its degradation time is relatively short, it is unfavorable for animal or skeleton healing.
The content of the invention
The object of the present invention is to provide a kind of polyglycolic acid resin composite material and its manufacturing method, in order to solve the class
It inscribes and has carried out sharp study, to solve mobility of the polyglycolic acid composite material in forming process, on the one hand need to reduce
The crystallinity of polyglycolic acid composite material, still further aspect on the basis of its mechanical performance is not reduced, suitably enhance addition
Material, meanwhile, reinforcing material is surface-treated.By select the molecular weight of appropriate polyglycolic acid, melt viscosity and
Molecular weight distribution index meets the performance of polyglycolic acid composite material process planning control parameter and polyglycolic acid composite material
Feature disclosure satisfy that animal or the medical fracture fixation material of human body surgery, tissue engineering bracket, suture supporting material
It needs, especially as the increase of polyglycolic acid molecular weight, melt viscosity also increases therewith, and melt flow rate (MFR) reduces therewith,
The screw torque of double screw extruder can also increased, the present invention is in order to solve the problems, such as this series, by the excellent of technological parameter
Change, animal or fracture fixation material, tissue engineering bracket, suture reinforcing material needed for human body surgery can be met by producing
Material.
The purpose of the present invention is what is realized by the following means.
A kind of polyglycolic acid resin composite material, the polyglycolic acid resin composite material contain 30~40%wt polyglycolic acids
Resin, 20~30%wt inorganic filling materials and 30~50% reinforcing material.
The preferred 34%wt polyglycolic acid resins of the polyglycolic acid resin composite material, 26%w inorganic filling materials and 40%wt
Reinforcing material.
The inorganic filling material is nano level titanium dioxide powder or nano level magnesium oxide powder.
The reinforcing material is polyetheretherketonefiber fiber or polyphenyl nylon；The polyphenyl nylon is the short of 3~6mm
Fiber.
The present invention also provides a kind of manufacturing method of polyglycolic acid resin composite material, using following technique process：
（1）Add in the inorganic filling material of nano level titanium oxide or alundum (Al2O3) or magnesium oxide powder containing 0.3~
The ethanol solution of 0.6%wt Ethoxysilanes under the stirring of homogenizer, is uniformly mixed, and inserts temperature as 80~90
DEG C exhaust baking oven in, by inorganic filling material dry 2~3h；
（2）By step（1）Processed inorganic filling material, it is 200,000~400,000 to add in weight average molecular weight, molecular weight distribution system
Number is in 1.8~1.88 polyglycolic acid resin, and 30~45min is stirred in homogenizer；
（3）By step（2）The obtained polyglycolic acid resin containing organic and/or inorganic materials and the nothing with 0.3~0.6%wt Ethoxysilanes
The processed polyetheretherketonefiber fiber of hydrous ethanol solution or polyphenyl nylon reinforcing material, wherein polyphenyl nylon are 3~6mm
Staple fiber, after input single screw extrusion machine honey refining, composite material directly inputs double through single screw extrusion machine head melt pipe
The feed inlet of screw extruder, by double screw extruder further honey refining by its extrusion die be extruded into grain size for 2~
3mm, a length of 4~6mm composite material granulars.
（4）By step（3）The polyglycolic acid composite material of obtained extrusion molding inserts the vacuum that temperature is 80~90 DEG C
In baking oven, dry 18~for 24 hours；
（5）Dried polyglycolic acid composite material is inputted in injection molding machine, is 30~40 in the feed pot implantation temperature of injection molding machine
DEG C, moisture is 0.001~0.003% drying nitrogen, and polyglycolic acid composite material is molded into animal skeleton by injection molding machine
Augment material or fracture fixation material.
The material simulation human body or animal body fluid environment preserve 3 months after, polyglycolic acid resin composite material
Degradation rate is 10~40%wt.
Beneficial effects of the present invention：
In the technological process of the present invention, since polyglycolic acid resin is linear molecular chain structure, meanwhile, by the shadow of molecular weight
It rings, to obtain the relatively good composite material of mobility, on the one hand suitably to select the size of weight average molecular weight, on the other hand also
The breadth coefficient of selection molecular weight is needed, if weight average molecular weight selects larger polyglycolic acid resin, melt flow rate (MFR)
Relatively small, melt viscosity will be relatively large, is on the one hand unfavorable for the machine-shaping of polyglycolic acid composite material, in addition can
Increase the screw torque of double screw extruder, in turn result in power consumption increase；If select weight average molecular weight relatively small
Polyglycolic acid resin, fluidity of molten is relatively preferable, although the relatively small polyglycolic acid resin of this weight average molecular weight has
Beneficial to machine-shaping, still, the mechanical strength of module cannot meet the needs again, and therefore, the present invention has found by experiment repeatedly,
Polyglycolic acid resin of the weight average molecular weight in the range of 20~400,000 can not only meet the relatively good requirement of melt flows, but also
Meet the requirement of polyglycolic acid composite material machinery performance.
Certainly, to solve deficiency of the previous polyglycolic acid composite material in forming processing technology, the present invention is poly- except selecting
Outside the weight average molecular weight of ethyl alcohol acid resin, it is also necessary to the breadth coefficient of molecular weight is selected, if the breadth coefficient of molecular weight is too
Narrow, the fluidity of molten of the polyglycolic acid resin of onesize weight average molecular weight is relatively poor, is unfavorable for polyglycolic acid composite wood
The machine-shaping of material if molecular weight distribution index is too wide, and can cause polyglycolic acid resin composite material in process
It collapses or shaped crystalline rate is widely different, meanwhile, the inside of section bar can also be caused to occur that hole etc. is not fine and close etc. to be lacked
It falls into, for this purpose, in the process of the present invention, by testing discovery repeatedly, selecting molecular weight distribution index in the range of 3.6~4.8
Polyglycolic acid resin can either meet the requirement for being easily worked shaping, and the requirement of section bar compactness can be met, while can also
Meet the requirement of polyglycolic acid resin composite material machinery performance.
In the process of the present invention, due to needing to select the relatively wide polyglycolic acid resin of molecular weight distribution index, just
The certain mechanical performance of polyglycolic acid resin composite material can be sacrificed, in order to make up because wider molecular weight distribution index is selected to make
Into the deficiency in polyglycolic acid resin composite material machinery performance, it is necessary to be properly added and life in polyglycolic acid resin composite material
The preferable reinforcing material of object compatibility, although in high molecular material, the material with biocompatibility has more than 90 kinds,
It is influenced by various aspects such as its performances, it is necessary to made choice to reinforcing material, is particularly suitable for animal or skeleton supplement
On the one hand the biocompatible material of material or fracture fixation material needs such material to have biocompatibility, still further aspect
It also needs to human body not caused to damage after such material is degraded in animal or human body, there are one this kind of biocompatibility materials of aspect
Material does not damage human body in the case of non-degradable in animal or human body, meanwhile, can both it increase there are one aspect
The mechanical strength of polyglycolic acid resin composite material, and can be in favor of machine-shaping, therefore, the present invention is by experiment hair repeatedly
It is existing, it may be used as reinforcing material and with biocompatibility, while the enhancing that human body will not also be caused to damage to animal or human body
Material is polyetheretherketonefiber fiber or polyphenyl acyl ammonia fiber, since polyphenyl acyl ammonia fiber is influenced by self-characteristic, it is necessary to be grown
Line is the staple fiber for being chopped into certain length, could meet the needs of the present invention.
In addition, in the process of the present invention, according to actual needs, a certain number of inorganic nano materials can also be added,
While the purpose is to further improve the mechanical performance of polyglycolic acid resin composite material, it can also make up to a certain extent
Deficiency caused by select wider molecular weight distribution index in polyglycolic acid resin composite material machinery performance, the present invention's
In the process, have been found that only addition reinforcing material, do not add nano inorganic material, the synthesis of polyglycolic acid resin composite material
Mechanical performance is relatively low compared with the situation that two kinds of materials add, for this purpose, on the one hand in order to meet the present invention polyglycolic acid tree
The needs of resin composite material mechanical performance, on the other hand, it is also necessary to meet the section bar manufactured by polyglycolic acid resin composite material,
When for animal or human skeleton supporting material or fracture fixation material, human body will not be damaged, therefore, the present invention
By testing discovery repeatedly, the inorganic nano material that can be added is titanium oxide and magnesia.
In the process of the present invention, on the basis of polyglycolic acid resin molecular weight and molecualr weight distribution coefficient is selected, also
The inorganic nano material and high molecular material of selection addition certain percentage, it is compound its purpose is to improve polyglycolic acid resin
The comprehensive mechanical performance of material, had not only met the needs of machine-shaping, but also met for animal or skeleton supporting material
Or the needs of the mechanical strength needed for fracture fixation material.
In the process of the present invention, since the molecular weight of the polyglycolic acid resin of selection is relatively high, melt flows speed
Rate is relatively low, and melt viscosity is larger, in order to meet the needs of machine-shaping, it is necessary to be squeezed using single screw extrusion machine and twin-screw
Machine series connection is gone out further to carry out sweet refining to polyglycolic acid resin composite material, meanwhile, in order to make the polyglycolic acid tree after honey refining
Resin composite material particle is readily processible to various moulded parts, in process using injection molding machine come pressure when improving injection molding
Power solves the difficulty of the machine-shaping caused by polyglycolic acid resin melt flows are relatively small, and solves because of polyethanol
Acid resin molecular weight distribution relatively wide the defects of causing moulded parts.
In process, the purpose using the drying nitrogen of certain temperature is prevented by dried poly- second to the present invention
Alkyd resin composite material, the moisture absorption caused by due to ingress of air, in turn resulting in inside moulded parts has the defects of cavity to generate.
The present invention can be used for animal or skeleton supporting material or/and fracture fixation material to develop, right first
All reinforcing materials and inorganic filling material carry out coupling processing, and purpose makes reinforcing material and inorganic filling material and poly- second
Alkyd resin is fully compatible, simultaneously as polyglycolic acid resin when aoxidizing heat cross-linking and sliding chemical crosslinking there are certain difficulty,
And in order under conditions of the toughness of polyglycolic acid resin is not reduced, be carried out to reinforcing material and inorganic filler at coupling
Reason.
In addition, of the invention since the molecular weight distribution index of selection polyglycolic acid resin is relatively wide, low molecule therein
Polymer is relatively more compared with the narrow polyglycolic acid resin of molecular weight distribution index, since the boiling point of low polymer is opposite
It is relatively low, so when single screw extrusion machine and double screw extruder are kneaded, it is necessary to carry out one to polyglycolic acid resin composite material
Fixed devolatilization processing, i.e., the extraction of appropriate heating interval evaporates on single screw extrusion machine and double screw extruder low point
Sub- polyglycolic acid resin oligomer, after devolatilization processing, which is being processed into polyglycolic acid resin composite material
During molded article, the yield rate of molded article is not only improved, but also improves the mechanical strength between model, it is so also more favourable
In the healing of animal or skeleton.
The present invention uses the strengthening material of polyetheretherketonefiber fiber and polyphenyl nylon as polyglycolic acid resin composite material
Material, since this two classes reinforcing material has biocompatibility, even if human body group will not be caused by being decomposed in human body or animal body
The damage knitted, meanwhile, the human body or animal skeleton supporting material or fracture fixation material made using high molecular material with it is stainless
Steel or titanium material compare, and second of operation need not be carried out by, which having, takes out remnant, these remnants can be within a certain period of time
The advantages that slowly being excreted by decomposing, being more advantageous to animal or skeleton healing.
The polyglycolic acid resin composite material of the present invention has excellent biological degradability, in order to know polyglycolic acid resin
The biological degradability of composite material after 3 months, measures poly- second, it is necessary to simulate the fluid environment of human body or animal organism
The degree of alkyd resin composite degradation, if palliating degradation degree is more than 40%wt, the degradation speed of polyglycolic acid resin composite material
Rate is too fast, is unfavorable for the healing of animal or skeleton, if palliating degradation degree is less than 10%, polyglycolic acid resin composite material
Degradation rate is excessively slow, the appropriate activity being unfavorable for after skeleton healing, in order to obtain the polyglycolic acid consistent with the present invention
Resin composite materials are, it is necessary to select appropriate molecular weight and molecualr weight distribution coefficient.
Description of the drawings
What Fig. 1 was represented is polyglycolic acid composite material part performance indicator.
Specific embodiment
The brief description of the process of the present invention：
The ethanol solution containing a certain amount of Ethoxysilane is added in inorganic filling material, in the stirring of homogenizer
Under, it is uniformly mixed, inserts in the exhaust baking oven of certain temperature, after inorganic filling material is dried certain time, be added to Sheng
Have and the time is stirred in the homogenizer of certain molecular weight polyglycolic acid resin, when inorganic filling material and polyglycolic acid resin
After being sufficiently mixed uniformly, after single screw extrusion machine honey refining is inputted together with reinforcing material, composite material is through single screw extrusion machine
Head melt pipe directly inputs the feed inlet of double screw extruder, is refined by double screw extruder is further sweet by head die
Have extrusion molding, obtain polyglycolic acid resin composite material granular, the particle is after the drying process before overmolding, input note
Molded article is molded into molding machine, which may be used as animal or skeleton supporting material or fracture fixation material.
The technique of the present invention is described in further detail with reference to embodiment.
Embodiment 1
The ethanol solution containing 0.6%wt Ethoxysilanes is added in nano level titanium dioxide powder, in homogenizer
Stirring under, be uniformly mixed, insert it is at a temperature of 90 °C exhaust baking oven in, inorganic filling material drying 2h after, addition fills
30min is stirred in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 400,000, molecular weight distribution index is 1.8；With
With the processed polyetheretherketonefiber fiber reinforcing material of the ethanol solution of 0.3%wt Ethoxysilanes, single screw extrusion machine is inputted
After honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Further honey refining by its extrusion die extrusion molding, obtains grain size and is answered for 2mm, the polyglycolic acid of a length of 4mm double screw extruder
Condensation material particle is inserted in the vacuum drying oven that temperature is 80 DEG C, after dry 18h；It inputs in injection molding machine, in the feed pot of injection molding machine
The drying nitrogen that implantation temperature is 30 DEG C, moisture is 0.001%, polyglycolic acid composite material are molded into mould by injection molding machine
Product.Wherein polyglycolic acid resin composite material contain the nano level titanium dioxide powder of 40%wt polyglycolic acid resins, 30%wt without
The reinforcing material of machine packing material and 30%wt polyetheretherketonefiber fibers.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 10%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Embodiment 2
The ethanol solution containing 0.3%wt Ethoxysilanes is added in nano level titanium dioxide powder, in homogenizer
Stirring under, be uniformly mixed, it is in 80 DEG C of exhaust baking oven to insert temperature, and after inorganic filling material drying 3h, addition fills
Weight average molecular weight is 200,000, and molecular weight distribution index is to stir 45min in the homogenizer of 1.88 polyglycolic acid resin；With
With the processed polyetheretherketonefiber fiber reinforcing material of the ethanol solution of 0.6%wt Ethoxysilanes, single screw extrusion machine is inputted
After honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Further honey refining by its extrusion die extrusion molding, obtains grain size and is answered for 3mm, the polyglycolic acid of a length of 6mm double screw extruder
Condensation material particle, inserting temperature is in 80~90 DEG C of vacuum drying oven, dry 18~for 24 hours after；It inputs in injection molding machine, in injection molding machine
Feed pot implantation temperature be 30~40 DEG C, the drying nitrogen that moisture is 0.001~0.003%, polyglycolic acid composite material
Moulded parts is molded by injection molding machine.Contain 30%wt polyglycolic acid resins, 20%wt nanoscales in the polyglycolic acid composite material
Titanium dioxide powder inorganic filling material and 50%wt polyetheretherketonefiber fiber reinforcing material.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 40%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Embodiment 3
The ethanol solution containing 0.6%wt Ethoxysilanes is added in the nano level magnesium oxide powders of 30%wt, at a high speed
It under the stirring of mixer, is uniformly mixed, inserts in the exhaust baking oven that temperature is 80 DEG C, after inorganic filling material drying 3h, add
It is stirred in the homogenizer for entering to fill the polyglycolic acid resin that weight average molecular weight is 200,000, molecular weight distribution index is 1.88
45min；With the processed polyphenyl nylon reinforcing material of ethanol solution with 0.6%wt Ethoxysilanes, single spiral shell is inputted
After the honey refining of bar extruder, composite material directly inputs the charging of double screw extruder through single screw extrusion machine head melt pipe
Mouthful, by double screw extruder further honey refining by its extrusion die extrusion molding, obtain grain size for 2mm, a length of 4mm it is poly-
Glycolic composite material granular is inserted in the vacuum drying oven that temperature is 80 DEG C, after drying for 24 hours；It inputs in injection molding machine, in injection molding machine
Feed pot implantation temperature be 40 DEG C, the drying nitrogen that moisture is 0.003%, polyglycolic acid composite material pass through injection molding machine
It is molded into moulded parts.Contain 40%wt polyglycolic acid resins, the nano level magnesia of 30%wt in the polyglycolic acid composite material
The polyphenyl amide fiber reinforced materials of powder inorganic filling material and 30%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 40%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Comparison example 1：
The ethanol solution containing 0.6%wt Ethoxysilanes is added in nano level titanium dioxide powder, in homogenizer
Stirring under, be uniformly mixed, insert it is at a temperature of 90 °C exhaust baking oven in, inorganic filling material drying 2h after, addition fills
30min is stirred in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 500,000, molecular weight distribution index is 1.88；With
With the processed polyphenyl nylon reinforcing material of the ethanol solution of 0.6%wt Ethoxysilanes, single screw extrusion machine is inputted
After honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Further honey refining by its extrusion die extrusion molding, obtains grain size and is answered for 2mm, the polyglycolic acid of a length of 4mm double screw extruder
Condensation material particle is inserted in the vacuum drying oven that temperature is 80 DEG C, after drying for 24 hours；It inputs in injection molding machine, in the feed pot of injection molding machine
The drying nitrogen that implantation temperature is 40 DEG C, moisture is 0.003%, polyglycolic acid composite material are molded into mould by injection molding machine
Product.It is inorganic containing 30%wt polyglycolic acid resins, the nano level titanium dioxide powders of 20%wt in the polyglycolic acid composite material
The polyphenyl nylon reinforcing material of packing material and 50%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 8%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Embodiment 4
The ethanol solution containing 0.3%wt Ethoxysilanes is added in nano level magnesium oxide powder, in homogenizer
Stirring under, be uniformly mixed, insert it is at a temperature of 90 °C exhaust baking oven in, inorganic filling material drying 2h after, addition fills
30min is stirred in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 400,000, molecular weight distribution index is 1.8；With
With the processed polyetheretherketonefiber fiber reinforcing material of the ethanol solution of 0.6%wt Ethoxysilanes, single screw extrusion machine is inputted
After honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Further honey refining by its extrusion die extrusion molding, obtains grain size and is answered for 3mm, the polyglycolic acid of a length of 6mm double screw extruder
Condensation material particle is inserted in vacuum drying oven at a temperature of 90 °C, after dry 18h；It inputs in injection molding machine, in the feed pot of injection molding machine
The drying nitrogen that implantation temperature is 30 DEG C, moisture is 0.001%, polyglycolic acid composite material are molded into mould by injection molding machine
Product.In the polyglycolic acid composite material containing 40%wt polyglycolic acid resins, 20%wt nano level magnesium oxide powder without
The polyetheretherketonefiber fiber reinforcing material of machine packing material and 40%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 10%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Embodiment 5
The ethanol solution containing 0.4%wt Ethoxysilanes is added in nano level titanium dioxide powder, in homogenizer
Stirring under, be uniformly mixed, it is in 83 DEG C of exhaust baking oven to insert temperature, after inorganic filling material drying 2.6h, adds in and contains
Have in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 330,000, molecular weight distribution index is 1.83 stirring 30~
45min；With the processed polyetheretherketonefiber fiber fibre reinforced materials of ethanol solution with 0.4%wt Ethoxysilanes, input
Single screw extrusion machine honey refining after, composite material through single screw extrusion machine head melt pipe directly input double screw extruder into
Material mouth, by double screw extruder, further honey is refined by its extrusion die extrusion molding, it is 2.5mm, a length of 4mm to obtain grain size
Polyglycolic acid composite material granular, it is in 86 DEG C of vacuum drying oven, after dry 21h to insert temperature；It inputs in injection molding machine, is noting
The drying nitrogen that the feed pot implantation temperature of molding machine is 33 DEG C, moisture is 0.002%, polyglycolic acid composite material is by note
Molding machine is molded into moulded parts.Contain 34%wt polyglycolic acid resins, the nano level oxidations of 26%wt in the polyglycolic acid composite material
The polyetheretherketonefiber fiber reinforcing material of titanium powder inorganic filling material and 40%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 16%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Embodiment 6
The ethanol solution containing 0.5%wt Ethoxysilanes is added in nano level magnesium oxide powder, in homogenizer
Stirring under, be uniformly mixed, it is in 88 DEG C of exhaust baking oven to insert temperature, after inorganic filling material drying 2.8h, adds in and contains
Have in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 280,000, molecular weight distribution index is 1.86 and stir 39min；
With the processed polyphenyl nylon reinforcing material of ethanol solution with 0.5%wt Ethoxysilanes, Single screw extrusion is inputted
After machine honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Crossing double screw extruder, further honey refining by its extrusion die extrusion molding, obtains grain size as 3mm, the polyethanol of a length of 5.5mm
Sour composite material granular is inserted in the vacuum drying oven that temperature is 81 DEG C, after dry 23h；It inputs in injection molding machine, in adding for injection molding machine
The drying nitrogen that batch can implantation temperature is 38 DEG C, moisture is 0.0016%, polyglycolic acid composite material are molded by injection molding machine
Into moulded parts.In the polyglycolic acid composite material containing 33%wt polyglycolic acid resins, the nano level magnesia powders of 28%wt without
The polyphenyl nylon reinforcing material of machine packing material and 39%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 36.3%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Comparison example 2：
The ethanol solution containing 0.4%wt Ethoxysilanes is added in nano level magnesium oxide powder, in homogenizer
Stirring under, be uniformly mixed, it is in 83 DEG C of exhaust baking oven to insert temperature, after inorganic filling material drying 2.6h, adds in and contains
Have in the homogenizer for the polyglycolic acid resin that weight average molecular weight is 150,000, molecular weight distribution index is 2.6 and stir 38min；
With the processed polyphenyl nylon reinforcing material of ethanol solution with 0.4%wt Ethoxysilanes, Single screw extrusion is inputted
After machine honey refining, composite material directly inputs the feed inlet of double screw extruder through single screw extrusion machine head melt pipe, is passing through
Crossing double screw extruder, further honey refining by its extrusion die extrusion molding, obtains grain size as 2mm, the polyglycolic acid of a length of 4mm
Composite material granular is inserted in the vacuum drying oven that temperature is 84 DEG C, after dry 22h；It inputs in injection molding machine, in the charging of injection molding machine
The drying nitrogen that tank implantation temperature is 36 DEG C, moisture is 0.0021%, polyglycolic acid composite material are molded by injection molding machine
Moulded parts.In the polyglycolic acid composite material containing 39%wt polyglycolic acid resins, the nano level magnesium oxide powders of 23%wt without
The polyphenyl nylon reinforcing material of machine packing material and 38%wt.
The material is after simulation human body or animal body fluid environment preserve 3 months, the drop of polyglycolic acid resin composite material
Solution rate is 80.1%wt.
The polyglycolic acid resin composite material of acquisition, part performance characteristic are listed in Fig. 1.
Claims (6)
1. a kind of polyglycolic acid resin composite material, it is characterised in that：The polyglycolic acid resin composite material contains 30~40%
Wt polyglycolic acid resins, 20~30%wt inorganic filling materials and 30~50% reinforcing material.
2. polyglycolic acid resin composite material according to claim 1, it is characterised in that：The inorganic filling material is to receive
The titanium dioxide powder of meter level or nano level magnesium oxide powder.
3. polyglycolic acid resin composite material according to claim 1, it is characterised in that：The reinforcing material is polyethers ether
Ketone fiber or polyphenyl nylon；The polyphenyl nylon is the staple fiber of 3~6mm.
4. a kind of manufacturing method of polyglycolic acid resin composite material as claimed any one in claims 1 to 3, feature exist
In comprising the following steps：
（1）The ethanol solution containing 0.3~0.6%wt Ethoxysilanes is added in inorganic filling material, in high-speed stirred
It under the stirring of machine, is uniformly mixed, inserts in the exhaust baking oven that temperature is 80~90 DEG C, inorganic filling material is dried into 2~3h；
（2）By step（1）Processed inorganic filling material adds in weight average molecular weight as 20~400,000, molecular weight distribution index
For in 1.8~1.88 polyglycolic acid resin, 30~45min is stirred in homogenizer；
（3）By step（2）The obtained polyglycolic acid resin containing organic and/or inorganic materials and the nothing with 0.3~0.6%wt Ethoxysilanes
The processed reinforcing material of hydrous ethanol solution, after input single screw extrusion machine honey refining, composite material is through single screw extrusion machine head
Melt pipe directly inputs the feed inlet of double screw extruder, is refined by double screw extruder is further sweet, by its head die
Has extrusion molding；
（4）By step（3）The polyglycolic acid composite material of obtained extrusion molding inserts the vacuum drying oven that temperature is 80~90 DEG C
In, dry 18~for 24 hours；
（5）By step（4）Dried polyglycolic acid composite material is inputted in injection molding machine, injects temperature in the feed pot of injection molding machine
The drying nitrogen for being 0.001~0.003% for 30~40 DEG C, moisture is spent, polyglycolic acid composite material is molded by injection molding machine
Into moulded parts.
5. the manufacturing method of polyglycolic acid resin composite material according to claim 4, it is characterised in that：Step（3）Institute
The product for the extrusion molding stated is composite material granular；The grain size of the composite material granular is 2~3mm, a length of 4~6mm.
6. the manufacturing method of polyglycolic acid resin composite material according to claim 4, it is characterised in that：Step（5）Institute
The moulded parts being molded by injection molding machine stated is the supplement material of animal skeleton or fracture fixation material；The material is being simulated
After human body or animal body fluid environment preserve 3 months, the degradation rate of polyglycolic acid resin composite material is 10~40%wt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111633946A (en) * | 2020-06-04 | 2020-09-08 | 中鸿纳米纤维技术丹阳有限公司 | Preparation method of polyglycolic acid with low melt viscosity |
| CN114829740A (en) * | 2019-12-18 | 2022-07-29 | 索尔维特殊聚合物美国有限责任公司 | Downhole tool components comprising branched poly (hydroxy acids) |
| CN115418092A (en) * | 2022-10-11 | 2022-12-02 | 道恩周氏(青岛)复合包装材料有限公司 | Polyglycolic acid material and preparation method and application thereof |
| CN115591015A (en) * | 2022-10-25 | 2023-01-13 | 季华实验室（Cn） | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007130648A2 (en) * | 2006-05-05 | 2007-11-15 | Ceramatec, Inc. | Fully or partially bioresorbable orthopedic implant |
| CN104684997A (en) * | 2012-10-11 | 2015-06-03 | 株式会社吴羽 | Polyglycolic acid resin composition, and method for producing same |
-
2017
- 2017-12-14 CN CN201711338935.0A patent/CN108079377A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007130648A2 (en) * | 2006-05-05 | 2007-11-15 | Ceramatec, Inc. | Fully or partially bioresorbable orthopedic implant |
| CN104684997A (en) * | 2012-10-11 | 2015-06-03 | 株式会社吴羽 | Polyglycolic acid resin composition, and method for producing same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114829740A (en) * | 2019-12-18 | 2022-07-29 | 索尔维特殊聚合物美国有限责任公司 | Downhole tool components comprising branched poly (hydroxy acids) |
| CN111633946A (en) * | 2020-06-04 | 2020-09-08 | 中鸿纳米纤维技术丹阳有限公司 | Preparation method of polyglycolic acid with low melt viscosity |
| CN115418092A (en) * | 2022-10-11 | 2022-12-02 | 道恩周氏(青岛)复合包装材料有限公司 | Polyglycolic acid material and preparation method and application thereof |
| CN115591015A (en) * | 2022-10-25 | 2023-01-13 | 季华实验室（Cn） | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
| CN115591015B (en) * | 2022-10-25 | 2024-01-26 | 季华实验室 | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
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