CN109501425B - A kind of medical X-ray-preventing composite material and preparation method - Google Patents
A kind of medical X-ray-preventing composite material and preparation method Download PDFInfo
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- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32—LAYERED PRODUCTS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
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Abstract
The present invention relates to a kind of medical X-ray-preventing composite material and preparation methods, belong to X-ray protection technical field.The present invention selects nanometer lanthanum hexaboride (LaB6) with high temperature resistant liquid crystal polyester composite as shielding material, solve the harm problem of heavy metal lead, obtained that preparation method is simple and flexible molding novel high polymer composite material；Simultaneously, the present invention is added in the modified copolyester of graphene using the nanometer lanthanum hexaboride modified, high temperature resistant liquid crystal polyester composite material of organic-treating, the processes such as melt drawn are carried out to which the controllable composite sheet of thickness be prepared, the composite sheet carries out multi hot press using hot press and obtains the good medical X-ray-preventing composite plate of comprehensive shielded property, and material is light, is convenient for operation.
Description
Technical field
The invention belongs to X-ray protection technical fields, more particularly to one kind to penetrate without lead, flexible molding medical anti-X
Line composite material and preparation method.
Background technique
X-ray is just increasingly being paid attention to the harm of human body by people, (such as medical treatment especially under many specific work environments
Checking process) staff require to dress special ray protective clothing, currently, the country usually by the treatment X of clinical use
Ray is divided into 3 kinds, i.e. contact treatment 10-60keV (0-1.0mmAl filter)；Superficial therapy 80-120ekV (1-1.4mmAl mistake
Filter disc) and depth therapy 150-400keV (0.5mmCu combined filtration piece), the staff in these environment requires to take
X-ray protection measure.
In general, X-ray protection takes, primary protection X-ray and gamma ray etc..In hospital radiological department, school experiment
The x-ray protective garment used under room, nuclear industry environment etc. is broadly divided into leaded protective garment (being all much micro- lead protection clothes at present)
With unleaded two class of protective garment.For low energy X ray, the products such as flint glass, organic glass and rubber are generally used, but it is this
Protective garment containing lead oxides has certain toxicity, not environmentally, so generally using concrete or by polypropylene and solid barrier
Agent compound fiber protects, but concrete quality weight, poor mobility.
For sigmatron, now popular is using resin/nanometer lead composite material and resin/nanometer sulfuric acid
Lead composite material.Lead (Pb), which is higher than ray between 88keV and 13-40keV to ability, a good absorbability, but for
There are a weak absorbing areas between the ray of 40-88keV for ability.Although lead composite material preferable, lead tolerance to X-ray shield
It is less, but it is not avoided that the precipitation of heavy metal lead and the harm to human body still.
To sum up, existing X-ray protection material still has quality weight, poor mobility and material and inherently has to human body
The problems such as evil；Therefore, it is anti-that a kind of simple preparation method, flexible molding, environmental protection, the good novel X-ray of comprehensive shielded property are found
Protective material becomes medical X-ray researcher's urgent problem to be solved.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide a kind of medical X-ray-preventing composite material and
Preparation method.The present invention selects nanometer lanthanum hexaboride (LaB6) with high temperature resistant liquid crystal polyester composite as shielding material,
It solves the harm problem of heavy metal lead, has obtained that preparation method is simple and flexible molding novel high polymer composite material；
Meanwhile the present invention is added graphene using the nanometer lanthanum hexaboride modified, high temperature resistant liquid crystal polyester composite material of organic-treating and changes
Property copolyester in, carry out the processes such as melt drawn to which the controllable composite sheet of thickness be prepared, composite sheet benefit
Multi hot press is carried out with hot press and obtains the good medical X-ray-preventing composite plate of comprehensive shielded property, and material is light, is convenient for operation.
An object of the present invention is to provide a kind of preparation method of X-ray-preventing composite material.
The second object of the present invention is to provide a kind of preparation method of X-ray-preventing composite plate.
The third object of the present invention is to provide a kind of X-ray-preventing composite inserting.
The fourth object of the present invention is to provide the application of above-mentioned X-ray-preventing composite inserting.
For achieving the above object, specifically, the invention discloses following technical proposals:
Firstly, the present invention discloses a kind of preparation method of X-ray-preventing composite material, include the following steps:
(1) lanthanum hexaboride powder and organic wax are mixed, organic-treating is carried out to lanthanum hexaboride using organic wax；
(2) by the lanthanum hexaboride powder and the smashed liquid crystal polyester powder of crystallizing and drying after organic-treating in step (1)
Disperse to mix after body mixing, it is spare；
(3) lanthanum hexaboride and liquid crystal polyester mixture that step (2) obtains are added in extruder and are melted, after by
Filter, spinneret, underwater cutpellet, infra-red drying obtain the modified liquid crystal polyester of lanthanum hexaboride, spare；Modified purpose is to utilize six boronations
Lanthanum powder acts on the strong absorption of X-ray and radiation shield, and high temperature resistant liquid crystal polyester after the carrier of lanthanum hexaboride as can make to change
Property after lanthanum hexaboride be also equipped with good heat resistance and radiation resistance simultaneously.
(4) by terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4 cyclohexane dimethanol (CHDM), 1,4- butanediol
(BDO) and after graphene mixing, catalyst, stabilizer progress esterification is added, then carries out polycondensation reaction under vacuum, obtains
The amorphous copolyester modified to graphene, it is spare；The purpose of the modified amorphous copolyester of black alkene is: the shape inside amorphous polyester
At electric thermal conductance, the heat being converted because shielding and absorbing X-ray is transmitted.Graphene is stratiform carbon structure, the graphite of stacking
Alkene has good electrical and thermal conductivity and X-ray radiation barrier property.Amorphous polyester and liquid crystal polyester have good compatibility,
The hot formability that can reduce liquid crystal polyester is added.
(5) the graphene modification for obtaining the modified liquid crystal polyester of lanthanum hexaboride that step (3) obtains and step (4) is non-
The mixing of brilliant copolyester, after crystallized drying through melting extrusion, melt longitudinal stretching, be cooled and shaped to get.
In step (1), the particle size range of the lanthanum hexaboride powder is 10~100nm.
In step (1), the purity of the lanthanum hexaboride is greater than 99.5%, the too low absorption that will affect X-ray of purity and screen
Cover effect.
In step (1), organic wax be carbon atom number be about 20~30 hydrocarbon mixture, ultra-low molecular weight northylen
One or more of wax, silane coupling agent；Preferably, organic wax is silane coupling agent.
In step (1), the organic-treating refers to: high under 1000-6000 revs/min of speed with high speed disperser
Speed dispersion 30-300 minute, it is therefore an objective to so that lanthanum hexaboride powder surface is sufficiently adsorbed organic wax, be convenient for it is contour in liquid crystal polyester
It is uniformly dispersed in molecular material.
In step (2), the weight ratio of the lanthanum hexaboride and liquid crystal polyester is 5~10:90~95.
In step (2), the liquid crystal polyester includes polyacrylic acid (virtue) ester, polymethylacrylic acid (virtue) esters, gathers to hydroxyl
One of yl benzoic acid ester, aromatic polyester (homopolymer or copolymer) are a variety of；Because X-ray is after being absorbed and shielding
It has more heat to occur, therefore, the present invention selects above-mentioned high temperature resistant liquid crystal polyester.
In step (2), the dispersion mixing refers to: dispersing 10~60 minutes under 2000~6000 revs/min of revolving speed.
In step (2), the fusing point of the liquid crystal polyester is 290~320 DEG C, and crystallizing and drying temperature is 140~170 DEG C, is done
The dry time is 3-7h.
In step (3), the fusion temperature is 250~350 DEG C.
In step (3), the extruder is the double screw extruder of 28~44:1 of draw ratio.
In step (3), the moisture content of the modified liquid crystal polyester of the lanthanum hexaboride is less than 0.04%.Moisture content is too high
The a large amount of decomposition that will cause liquid crystal polyester during the fusion plastification of twin-screw, reduce the mechanical property of liquid crystal polyester.
In step (4), the terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4-CHDM (CHDM), Isosorbide-5-Nitrae-
The weight ratio of butanediol (BDO) and graphene is 40~60:15~30:10~20:5~10:1~10.
In step (4), the catalyst is Mono-n-butyltin, Dibutyltin oxide, Dibutyltin oxide chloride, two
Butyl tin dilaurate tin, dibutyl tin acetate, monobutyl-tin-trichloride, three oxidation two tin, aluminum-based catalyst, germanium oxide, two
Two or more in titanium oxide, antimony oxide, antimony glycol or antimony acetate, because single catalyst is in the contracting of polymerization reaction
The poly- stage cannot achieve abundant polycondensation and obtain the polymer of high quality.
In step (4), on the basis of the catalyst amount is acid system (terephthalic acid (TPA)) total weight in reaction system
250~950ppm.
In step (4), the stabilizer be phenolic antioxidant, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate,
Phosphite ester, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, two or more in thioesters, because single stabilizer exists
The polycondensation phase of polymerization reaction is unable to get the preferable polymer of form and aspect.
In step (4), on the basis of the stabilizing agent dosage is acid system (terephthalic acid (TPA)) total weight in reaction system
250~800ppm.
In step (4), the temperature of the esterification is 240~270 DEG C, the time are as follows: 60~160 minutes.
In step (4), the condition of the polycondensation reaction are as follows: 275~295 DEG C of vacuum degree 10-30Pa, temperature, time is
120-180 minutes.
In step (4), the inherent viscosity of the modified amorphous copolyester of the graphene is 0.75~0.85dl/g.
In step (4), the fusing point of the modified amorphous copolyester of the graphene is 180~240 DEG C.
In step (5), the ratio for the amorphous copolyester that the modified liquid crystal polyester of the lanthanum hexaboride and graphene are modified
Are as follows: 40~80:20~60, mass fraction；
In step (5), the crystals dried mode is dry for vacuum drum, and 100~140 DEG C of temperature, the time 12~36
Hour.
In step (5), the temperature of the melting extrusion is 240~320 DEG C.
Secondly, the present invention discloses a kind of preparation method of X-ray-preventing composite plate, include the following steps:
S1: the liquid crystal polyester that the lanthanum hexaboride that step (3) obtains is modified and the graphene that step (4) obtains are modified non-
Composite sheet is made through melting extrusion, melt longitudinal stretching, cooling and shaping after crystallized drying in brilliant copolyester mixing, standby
With；
S2: by S1 composite sheet overlapping after preheat, be then pressed into type to get.
In step S1, the ratio for the amorphous copolyester that the modified liquid crystal polyester of the lanthanum hexaboride and graphene are modified
Are as follows: 40~80:20~60.
In step S1, the crystals dried mode is dry for vacuum drum, and 100~140 DEG C of temperature, the time 12~36 is small
When.
In step S1, the temperature of the melting extrusion is 240~320 DEG C.
In step S1, the composite sheet is with a thickness of 20~100 μm.
In step S2,5~20 layers are successively overlapped according to 60~90 ° of draw direction angle, through 150~240 DEG C of preheating 30
After~90min, using hot press under the pressure of 100~500MPa compression moulding to get thickness X-ray-preventing composite plate.
In step S2, the pressing forming time is 5~30min.
Again, the present invention discloses the X-ray-preventing composite plate of above method preparation, and the X-ray-preventing composite plate is according to thickness
It is different, it can be achieved that absorption to low energy X ray and sigmatron different-energy, reaches the shielding protection effect to X-ray.
Finally, the present invention discloses the X-ray-preventing composite plate of above method preparation in medicine, school experiment room, nuclear industry neck
Application in domain.
Compared with prior art, the beneficial effect that the present invention obtains is:
(1) then the present invention is added into using the nanometer lanthanum hexaboride modified, high temperature resistant liquid crystal polyester again of organic modification
In the modified amorphous copolyester of graphene, the processes such as melting extrusion, melt drawn are carried out under certain temperature and pressure and are obtained
To composite sheet, after obtained that thickness is controllable, realizes good shielding to different-energy X-ray by hot press multi hot press
X-ray-preventing composite plate, the composite inserting it is flexible molding, without heavy metal lead, environmental protection, light, thickness is controllable, convenient for production
And carrying；Meanwhile the preparation process of X-ray-preventing composite plate of the present invention is simple, the value of great industrialized production and practical application.
(2) X-ray-preventing composite plate prepared by the present invention can be inserted directly into needs during medicine needs taking X-ray
The textile fabric of the body position of protection, simplifies process, reduces requirement, easily facilitates medical staff's operation.
(3) the X-ray shield value of X-ray-preventing composite inserting prepared by the present invention can reach 95-99.9%, but thickness only has
With a thickness of 500~1000 μm, X-ray shield effect number, light weight is very suitable for user of service's wearing.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, existing X-ray protection material still has quality weight, poor mobility and material
The problems such as material is inherently harmful to the human body；Therefore, a kind of simple preparation method, flexible molding, environmental protection, comprehensive shielded property are found
Good novel X-ray protection material, becomes medical X-ray researcher's urgent problem to be solved.For this purpose, the present invention proposes one kind
Medical X-ray-preventing composite material and preparation method, the present invention is described further With reference to embodiment.
Embodiment 1
A kind of preparation method of X-ray-preventing composite plate, includes the following steps:
(1) select particle size range 10~50nm, purity for 99.9% lanthanum hexaboride powder, using organic wax high speed
High speed dispersion 210 minutes under 4000 revs/min of speed in dispersion machine；
(2) by the lanthanum hexaboride powder and the smashed high temperature resistant liquid crystal of crystallizing and drying after organic-treating in step (1)
Polyester powder disperses 10 minutes under 4000 revs/min of revolving speed by weight 10:90；The high temperature resistant liquid crystal polyester is fragrance
Adoption ester copolymer；The high temperature resistant liquid crystal melting point polyester is 298 DEG C, and between 150 DEG C, drying time is crystallizing and drying temperature
3h；
(3) twin-screw extrusion of draw ratio 36:1 is added in the lanthanum hexaboride and liquid crystal polyester mixture obtained step (2)
It is melted at 300 DEG C in machine, obtains six of moisture content less than 0.035% by filtering, spinneret, underwater cutpellet, infra-red drying
The modified high temperature resistant liquid crystal polyester of lanthanum boride, it is spare；
(4) by terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4 cyclohexane dimethanol (CHDM), 1,4- butanediol
(BDO), graphene is mixed by weight the ratio of 55:20:15:5:5, and composite catalyst, stabilizer is added in 240 DEG C of progress esters
Change reaction, after the vacuum degree of 10Pa, 295 DEG C at a temperature of carry out polycondensation reaction 120min, it is total to obtain the modified amorphous of graphene
Polyester；The inherent viscosity of the modified amorphous copolyester of the graphene is 0.80~0.85dl/g, and fusing point is 210~220 DEG C；
The composite catalyst is the mixture of dibutyl tin acetate and antimony glycol, and addition content is 950ppm；It is described compound steady
Determine the mixture that agent is phenolic antioxidant and phosphite ester, addition content is 800ppm；
(5) lanthanum hexaboride that step (3) is prepared modified high temperature resistant liquid crystal polyester and step (4) are prepared
The modified amorphous copolyester of graphene is mixed by the mass percent of 80:20, vertical through melting extrusion, melt after crystallized drying
To the composite sheet obtained after stretching, being cooled and shaped with a thickness of 50 μm；The crystallizing and drying temperature is 140 DEG C, and drying time is
12h, the moisture content after drying are 60~80ppm；The melting extrusion uses draw ratio for the double screw extruder of 32:1,
Extrusion temperature is 280 DEG C, and melt longitudinal stretching medium is 40 DEG C of air, draw roll use be 80 DEG C of roughness for 0.02~
The chrome-plated roller of 0.03um, melt longitudinal stretching ratio is 4.5:1；
(6) composite sheet that step (5) is prepared successively is overlapped 16 layers according to 60 ° of draw direction angle, through 240 DEG C
Preheating 30min after, suppress 20min under the pressure of 400MPa using hot press to get multiple with a thickness of 600 μm of X-ray-preventing
Plywood.
Embodiment 2
A kind of preparation method of X-ray-preventing composite plate, includes the following steps:
(1) selecting particle size range in 50~100nm, purity is 99.8~99.9% lanthanum hexaboride powder, and utilization is organic
Wax high speed dispersion 300 minutes under 6000 revs/min of speed in high speed disperser；Organic wax is silane coupling agent and surpasses
The mixture of low molecular weight polyethylene wax；
(2) the lanthanum hexaboride powder and the smashed high temperature resistant of crystallizing and drying after the organic-treating for obtaining step (1)
Liquid crystal polyester powder disperses 10 minutes under 6000 revs/min of revolving speed by weight 5:95；The high temperature resistant liquid crystal polyester is
Aromatic polyester copolymer；The high temperature resistant liquid crystal melting point polyester is 310 DEG C, and crystallizing and drying temperature is 140 DEG C, and drying time is
5h；
(3) twin-screw extrusion of draw ratio 28:1 is added in the lanthanum hexaboride and liquid crystal polyester mixture obtained step (3)
It is melted at 350 DEG C in machine, obtains six boron of the moisture content less than 0.03% by filtering, spinneret, underwater cutpellet, infra-red drying
Change the modified high temperature resistant liquid crystal polyester of lanthanum.
(4) by terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4 cyclohexane dimethanol (CHDM), 1,4- butanediol
(BDO) and graphene by weight 59:15:10:6:10 ratio mix, be added composite catalyst, stabilizer 270 DEG C into
Row esterification 60min, after the vacuum degree of 30Pa, 275 DEG C at a temperature of carry out polycondensation reaction 180min, it is modified to obtain graphene
Amorphous copolyester；The inherent viscosity of the modified amorphous copolyester of the graphene is 0.75~0.85dl/g, and fusing point is
180-200℃；The composite catalyst be dibutyl tin acetate and aluminum-based catalyst mixture, addition content be 400~
600ppm；The compound stabilizer is the mixture of phenolic antioxidant and trimethyl phosphate, and addition content is 300~500ppm；
(5) lanthanum hexaboride that step (3) is prepared modified high temperature resistant liquid crystal polyester and step (4) are prepared
The modified amorphous copolyester of graphene is mixed by the mass percent of 40:60, vertical through melting extrusion, melt after crystallized drying
To the composite sheet obtained after stretching, being cooled and shaped with a thickness of 100 μm；The crystallizing and drying temperature is 100 DEG C, and drying time is
36h, the moisture content after drying are 80ppm or less；The melting extrusion uses draw ratio for the double screw extruder of 40:1,
Extrusion temperature is 320 DEG C, and melt longitudinal stretching medium is 45 DEG C of air, draw roll use be 100 DEG C roughness for
The chrome-plated roller of 0.02um, melt longitudinal stretching ratio is 3:1；
(6) composite sheet that step (5) is prepared successively is overlapped 20 layers according to 90 ° of draw direction angle, through 150 DEG C
Preheating 90min after, suppress 30min under the pressure of 100MPa using hot press to get multiple with a thickness of 800 μm of X-ray-preventing
Plywood.
Embodiment 3
A kind of preparation method of X-ray-preventing composite plate, includes the following steps:
(1) selecting particle size range in 40~80nm, purity is 99.5~99.8% lanthanum hexaboride powder, utilizes organic wax
High speed dispersion 30 minutes under 1000 revs/min of speed in high speed disperser；Organic wax is silane coupling agent；
(2) by after step (1) organic-treating lanthanum hexaboride powder and the smashed high temperature resistant liquid crystal of crystallizing and drying it is poly-
Ester powder disperses 40 minutes under 2000 revs/min of revolving speed by weight 8:92；The high temperature resistant liquid crystal polyester is aromatic series
Polyester copolymer；The high temperature resistant liquid crystal melting point polyester is 320 DEG C, and crystallizing and drying temperature is 170 DEG C, and drying time is 7h；
(3) twin-screw of temperature draw ratio 44:1 is added in the lanthanum hexaboride and liquid crystal polyester mixture obtained step (2)
It is melted in extruder, obtains lanthanum hexaboride of the moisture content less than 0.035% by filtering, spinneret, underwater cutpellet, infra-red drying
Modified high temperature resistant liquid crystal polyester；
(4) by terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4 cyclohexane dimethanol (CHDM), 1,4- butanediol
(BDO) and graphene by weight 40:30:20:9:1 ratio mix, be added composite catalyst, stabilizer 260 DEG C into
Row esterification, after the vacuum degree of 25Pa, 280 DEG C at a temperature of carry out polycondensation reaction to obtain the modified amorphous copolymerization of graphene poly-
Ester；The inherent viscosity of the modified amorphous copolyester of the graphene is 0.82~0.85dl/g, and fusing point is 220-240 DEG C；It is described
Composite catalyst is the mixture of Dibutyltin oxide and aluminum-based catalyst, and addition content is 250ppm；The compound stabilizer
For the mixture of phenolic antioxidant and triphenyl phosphate, addition content is 250ppm；
(5) graphene that the modified high temperature resistant liquid crystal polyester of the lanthanum hexaboride that step (3) obtains is obtained with step (4) is changed
Property amorphous copolyester mixed by the mass percent of 60:40, through melting extrusion, melt longitudinal stretching, cold after crystallizing and drying
But the composite sheet with a thickness of 20 μm is obtained after forming；The crystallizing and drying temperature is 100 DEG C, drying time 18h, after dry
Moisture content is 60ppm or less；The melting extrusion uses draw ratio for the double screw extruder of 44:1, and extrusion temperature is
240 DEG C, melt longitudinal stretching medium is 40 DEG C of air, and it is 70 DEG C of roughness for the chrome-plated roller of 0.03um that draw roll, which uses,
Melt longitudinal stretching ratio is 3.5:1；
(6) composite sheet that step (5) is prepared successively is overlapped 20 layers according to 75 ° of draw direction angle, through 180 DEG C
Preheating 50min after, it is compound to get the X-ray-preventing with a thickness of 650 μm that 5min is suppressed under the pressure of 500MPa using hot press
Plate.
Embodiment 4
A kind of preparation method of X-ray-preventing composite plate, includes the following steps:
(1) selecting particle size range in 50~70nm, purity is 99.8~99.9% lanthanum hexaboride powder, utilizes organic wax
High speed dispersion 100 minutes under 3000 revs/min of speed in high speed disperser；Organic wax be silane coupling agent with it is ultralow
The mixture of molecular weight polyethylene wax；
(2) the lanthanum hexaboride powder and the smashed high temperature resistant of crystallizing and drying after the organic-treating for obtaining step (1)
Liquid crystal polyester powder disperses 30 minutes under 3000 revs/min of revolving speed by weight 7:93；The high temperature resistant liquid crystal polyester is
Aromatic polyester copolymer；The high temperature resistant liquid crystal melting point polyester is 290 DEG C, and crystallizing and drying temperature is 160 DEG C, and drying time is
4h；
(3) twin-screw extrusion of draw ratio 30:1 is added in the lanthanum hexaboride and liquid crystal polyester mixture obtained step (3)
It is melted at 330 DEG C in machine, obtains six boron of the moisture content less than 0.03% by filtering, spinneret, underwater cutpellet, infra-red drying
Change the modified high temperature resistant liquid crystal polyester of lanthanum.
(4) by terephthalic acid (TPA) (PTA), ethylene glycol (EG), 1,4 cyclohexane dimethanol (CHDM), 1,4- butanediol
(BDO) and graphene is mixed by weight the ratio of 60:10:10:10:10, and composite catalyst, stabilizer is added at 250 DEG C
Carry out esterification 120min, after the vacuum degree of 15Pa, 280 DEG C at a temperature of carry out polycondensation reaction 150min, obtain graphene
Modified amorphous copolyester；The inherent viscosity of the modified amorphous copolyester of the graphene is 0.75~0.85dl/g, fusing point
It is 180-200 DEG C；The composite catalyst is the mixture of dibutyl tin acetate and aluminum-based catalyst, and addition content is
500ppm；The compound stabilizer is the mixture of phenolic antioxidant and trimethyl phosphate, and addition content is 500ppm；
(5) lanthanum hexaboride that step (3) is prepared modified high temperature resistant liquid crystal polyester and step (4) are prepared
The modified amorphous copolyester of graphene is mixed by the mass percent of 70:30, vertical through melting extrusion, melt after crystallized drying
To the composite sheet obtained after stretching, being cooled and shaped with a thickness of 60 μm；The crystallizing and drying temperature is 120 DEG C, and drying time is
18h, the moisture content after drying are 80ppm or less；The melting extrusion uses draw ratio for the double screw extruder of 40:1,
Extrusion temperature is 300 DEG C, and melt longitudinal stretching medium is 35 DEG C of air, and it is 80 DEG C of roughness for 0.02um that draw roll, which uses,
Chrome-plated roller, melt longitudinal stretching ratio is 4:1；
(6) composite sheet that step (5) is prepared successively is overlapped 5 layers according to 80 ° of draw direction angle, through 170 DEG C
Preheating 40min after, it is compound to get the X-ray-preventing with a thickness of 200 μm that 5min is suppressed under the pressure of 100MPa using hot press
Plate.
Performance test:
By test, the shielding rate of the X-ray for the X-ray-preventing composite plate that embodiment 1-3 is prepared is respectively 95.8~
97.7%, 98.8~99.9%, 96.8~99.1%, this X-ray-preventing composite plate can perform well in medical examination procedures
Protection to staff.The present invention can prepare the X-ray-preventing composite plate of 0.2~0.8mm of thickness, and compound under the thickness
Protective garment weight only 1~2kg of plate preparation, and traditional defense plate is prepared identical under identical or approximate shield effectiveness
Protective garment needs the plate of 20~30mm of thickness, and weight is up to 10~20kg, lead equivalent about 0.4~0.5mmPb.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (33)
1. a kind of preparation method of X-ray-preventing composite material, it is characterised in that: described method includes following steps:
(1) lanthanum hexaboride powder and organic wax are mixed, organic-treating is carried out to lanthanum hexaboride using organic wax；
(2) by after organic-treating in step (1) lanthanum hexaboride powder and the smashed liquid crystal polyester powder of crystallizing and drying it is mixed
Disperse to mix after conjunction, it is spare；
(3) lanthanum hexaboride and liquid crystal polyester mixture that step (2) obtains are added in extruder and are melted, by filtering,
Spinneret, underwater cutpellet, infra-red drying obtain the modified liquid crystal polyester of lanthanum hexaboride, spare；
(4) after mixing terephthalic acid (TPA), ethylene glycol, 1,4-CHDM, 1,4-butanediol and graphene, catalysis is added
Agent, stabilizer carry out esterification, then carry out polycondensation reaction under vacuum, obtain the modified amorphous copolyester of graphene,
It is spare；
(5) the modified amorphous of the graphene obtained the lanthanum hexaboride that step (3) obtains modified liquid crystal polyester and step (4) is total
Polyester mixing, after crystallized drying through melting extrusion, melt longitudinal stretching, be cooled and shaped to get.
2. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (1), described six
The particle size range of lanthanum boride powder is 10~100nm.
3. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (1), described six
The purity of lanthanum boride is greater than 99.5%.
4. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: described to have in step (1)
Machine wax is that carbon atom number is one of 20~30 hydrocarbon mixture, Ultra-low molecular weight polyethylene wax, silane coupling agent or several
Kind.
5. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: described to have in step (1)
Machineization processing refers to: with high speed disperser high speed dispersion 30-300 minutes under 1000-6000 revs/min of speed, it is therefore an objective to
Lanthanum hexaboride powder surface is set sufficiently to adsorb organic wax, convenient for being uniformly dispersed in liquid crystal polyester high molecular material.
6. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (2), described six
The weight ratio of lanthanum boride and liquid crystal polyester is 5~10:90~95.
7. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (2), described point
Scattered mixing refers to: dispersing 10~60 minutes under 2000~6000 revs/min of revolving speed.
8. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (2), the liquid
The fusing point of brilliant polyester is 290~320 DEG C, and crystallizing and drying temperature is 140~170 DEG C, and drying time is 3-7h.
9. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (2), the liquid
Brilliant polyester includes one of aromatic polyester homopolymer or copolymer or a variety of.
10. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: described molten in step (3)
Changing temperature is 250~350 DEG C.
11. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: described to squeeze in step (3)
Machine is the double screw extruder of 28~44:1 of draw ratio out.
12. the preparation method of X-ray-preventing composite material as described in claim 1, it is characterised in that: in step (3), described six
The moisture content of the modified liquid crystal polyester of lanthanum boride is less than 0.04%.
13. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the terephthalic acid (TPA), ethylene glycol, 1,4-CHDM, 1,4-butanediol and graphene weight ratio be 40~60:
15~30:10~20:5~10:1~10.
14. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the catalyst be Mono-n-butyltin, Dibutyltin oxide, Dibutyltin oxide chloride, dibutyl tin dilaurate,
Dibutyl tin acetate, monobutyl-tin-trichloride, three two tin of oxidation, aluminum-based catalyst, germanium oxide, titanium dioxide, three oxidations two
Two or more in antimony, antimony glycol or antimony acetate.
15. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the catalyst amount is 250~950ppm in reaction system on the basis of acid system total weight.
16. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the stabilizer is phenolic antioxidant, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate, phosphite ester, tricresyl phosphate
Methyl esters, dimethyl phosphate, triphenyl phosphate, two or more in thioesters.
17. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the stabilizing agent dosage is 250~800ppm in reaction system on the basis of acid system total weight.
18. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the temperature of the esterification is 240~270 DEG C, the time are as follows: 60~160 minutes.
19. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the condition of the polycondensation reaction are as follows: 275~295 DEG C of vacuum degree 10-30Pa, temperature, time are 120-180 minutes.
20. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the inherent viscosity of the modified amorphous copolyester of the graphene is 0.75~0.85dl/g.
21. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (4)
In, the fusing point of the modified amorphous copolyester of the graphene is 180~240 DEG C.
22. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (5)
In, the mass ratio for the amorphous copolyester that the modified liquid crystal polyester of the lanthanum hexaboride and graphene are modified are as follows: 40~80:20
~60.
23. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (5)
In, the crystals dried mode is dry for vacuum drum, and 100~140 DEG C of temperature, the time 12~36 hours.
24. such as the preparation method of the described in any item X-ray-preventing composite materials of claim 1-12, it is characterised in that: step (5)
In, the temperature of the melting extrusion is 240~320 DEG C.
25. a kind of preparation method of X-ray-preventing composite plate, it is characterised in that: described method includes following steps:
S1: the liquid crystal that the lanthanum hexaboride that step (3) obtains in the described in any item preparation methods of claim 1-24 is modified is poly-
The ester amorphous copolyester modified with the graphene that step (4) obtains mixes, longitudinal through melting extrusion, melt after crystallized drying
It stretches, be cooled and shaped, composite sheet is made, it is spare,
S2: by S1 composite sheet overlapping after preheat, be then pressed into type to get.
26. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: in step S1, six boron
Change the mass ratio for the amorphous copolyester that the modified liquid crystal polyester of lanthanum and graphene are modified are as follows: 40~80:20~60.
27. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: in step S1, the crystallization
Dry mode is dry for vacuum drum, and 100~140 DEG C of temperature, the time 12~36 hours.
28. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: in step S1, the melting
The temperature of extrusion is 240~320 DEG C.
29. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: described compound in step S1
Sheet thickness is 20~100 μm.
30. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: in step S2, according to stretching
60~90 ° of angular separation is successively overlapped 5~20 layers, after 150~240 DEG C of 30~90min of preheating, using hot press 100
Compression moulding is under the pressure of~500MPa to get X-ray-preventing composite plate.
31. the preparation method of X-ray-preventing composite plate as claimed in claim 25, it is characterised in that: in step S2, the compacting
Molding time is 5~30min.
32. the X-ray-preventing composite material that such as described in any item preparation methods of claim 1-24 obtain is in medicine, school experiment
Application in room, nuclear industry field.
33. the X-ray-preventing composite plate that such as described in any item preparation methods of claim 25-31 obtain is in medicine, school experiment
Application in room, nuclear industry field.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153389A (en) * | 1996-08-13 | 1997-07-02 | 张启馨 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
| CN1477150A (en) * | 2002-07-31 | 2004-02-25 | 住友金属矿山株式会社 | Mother material containing thermal radiation screerning component and thermal radiation screening transparent resin formed material and thermal radiction screening thansparent laminated material |
| CN102782769A (en) * | 2009-12-30 | 2012-11-14 | 射线防护产品股份有限公司 | A multi-layer light-weight garment material with low radiation buildup providing scattered-radiation shielding |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003347787A (en) * | 2002-05-23 | 2003-12-05 | Shin Etsu Chem Co Ltd | Electromagnetic wave absorbing composition |
| TWI369943B (en) * | 2009-09-23 | 2012-08-01 | Univ Nat Taiwan | Electromagnetic wave absorption component and electromagnetic wave absorption device |
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2018
- 2018-11-14 CN CN201811353511.6A patent/CN109501425B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153389A (en) * | 1996-08-13 | 1997-07-02 | 张启馨 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
| CN1477150A (en) * | 2002-07-31 | 2004-02-25 | 住友金属矿山株式会社 | Mother material containing thermal radiation screerning component and thermal radiation screening transparent resin formed material and thermal radiction screening thansparent laminated material |
| CN102782769A (en) * | 2009-12-30 | 2012-11-14 | 射线防护产品股份有限公司 | A multi-layer light-weight garment material with low radiation buildup providing scattered-radiation shielding |
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