CN1789319A - Rare earth modified leadless X-ray shielding plastic - Google Patents
Rare earth modified leadless X-ray shielding plastic Download PDFInfo
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- CN1789319A CN1789319A CN 200410098610 CN200410098610A CN1789319A CN 1789319 A CN1789319 A CN 1789319A CN 200410098610 CN200410098610 CN 200410098610 CN 200410098610 A CN200410098610 A CN 200410098610A CN 1789319 A CN1789319 A CN 1789319A
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Abstract
The invention relates the rare earth modified leadless X ray barrier plastic. The method comprises the following steps: carrying out surface treatment to one part of inorganic rare earth, carrying out organic reaction treatment to the other part of inorganic rare earth, adding the two parts of inorganic rare earth in proportion into plastic, and getting the modified leadless X ray barrier plastic. The invention is widely used in medical diagnosis X-ray production apparatus, X-ray diffractometer, emitter of electron microscope and personnel protection in the condition of X -ray existing.
Description
Technical field:
The present invention relates to a kind of rare earth modified leadless X-ray shielding plastic.
Background technology:
The present invention is that polymer composite use in the high shielding properties of preparation, the shielding of unleaded, light weight softish thin layer X ray, is used for projector and other protection with the occasion staff of X ray generation of medical diagnosis X radial ray machine, X-ray diffractometer, electron microscope.
The development of ray protection material, producing and apply, is one of emphasis of civilian healthy prevention work, also is the important component part of nuclear energy development field, military domain radiation protection.State's inner macromolecule antiradiation material is mainly based on plumbous rubber item.States such as America and Europe, Japan have succeeded in developing novel thermoplastic elastomer composite material, and this matrix material has the physical and mechanical properties height under the condition of identical ratio protective value, surface property is good, ageing-resistant, excellent properties such as dimensional stabilizing can also the heat seal ready-made clothes.Under the condition of identical weight,, can also improve the work-ing life and the shielding property of material to a certain extent if use urethane as base material.Develop the related production technology abroad, prepared very thin sheet material (minimum thickness can reach 0.3mm).The personal protection clothing of the compound manufacturing of single or multiple lift is quite soft.This based sheet mainly is used to make radioprotective clothings such as protection jacket, vest, integral protection clothing, its shortcoming be discrete state material still based on lead, and cost an arm and a leg.
Usually its energy of most photons of the medical diagnosis X radial that is produced by the following tube voltage of 120KVp is lower than 88.0KeV.At present, the discrete state material of domestic and international medical X-ray shielding material is still based on lead, barium and oxide compound thereof.But since plumbous in the ray scope of 40-88keV, absorb a little less than, plumbous in addition, the barium material is big to human body harm, so people attempt usually to replace lead to make matrix material with K layer ABSORPTION EDGE other yuan between 40-88keV.
The foreign study person successively attempts having used elements such as Cu, Sn, Sb, I, Ba.The K layer of element Cu, Sn, Sb and I absorbs energy and is respectively 9.0,29.2,30.5 and 33.1keV, and is far away apart from the lower limit of weak uptake zone, all can not finely play the effect that remedies the weak uptake zone of Pb.Element B a chemical property is active, can not can only use with compound form with simple substance form.In the compound of Ba, that the shared therein weight percent of Ba element is the highest is BaO, but the alkalescence of BaO is very strong, and chemical toxicity is very big, and costs an arm and a leg, and has reduced its use value.If select BaSO for use
4Though, can overcome the chemical toxicity of Ba, strengthen its chemical stability, because element B a accounts for weight percent low excessively (59%) in this compound, make the shield effectiveness variation.Therefore, up at present, generally still based on lead.
Russ P RU2054439, RU2028331 disclose the rubber X-ray-preventing matrix material with the modification of inorganic rare earth oxide filler, but because inorganic rare earth (rare earth oxide) and rubber matrix is compatible relatively poor, therefore at itself and polymeric matrix the space appears easily at the interface, these spaces will be easy to be passed through when energetic ray shines, even the phenomenon that ray occurs leaking, the shielding homogeneous performance of material also is difficult to guarantee, so the stability of material also is difficult to control.
From matrix polymer, developed country's roentgen machine ray shields such as the U.S. and Japan have been brought into use plastics (comprising thermoplastic elastomer) material, the main clothings such as protection jacket, vest, integral protection clothing of making.This material is compared with traditional elastomeric material, characteristics are very outstanding, most importantly in light weight, barrier propterty is good, long service life, soft comfortable, can also process as the working method of plastics, therefore can reclaim, thereby improved rare earth/plastic material service efficiency repeatedly effectively, and fully saved the rare earth resources of China.
Summary of the invention:
The purpose of this invention is to provide a kind of rare earth modified leadless X-ray shielding plastic, the part of inorganic rare earth is carried out surface modification treatment, another part reaction treatment that organises prepares organic RE salt, the two cooperates with certain proportion and adds in the plastics, thereby obtain modified leadless X-ray shielding plastic, make the shielding properties of material, mechanical property all reach the ideal effect.
A kind of rare earth modified leadless X-ray shielding plastic, it is formed and parts by weight are:
Plastics 50-100
Organic rare-earth ligand 20-200
Inorganic rare earth compound 20-500
Tenderizer 2-30
Oxidation inhibitor 1-3
Silane coupling agent 0.5-3
Used plastics are polyolefine (polyethylene, ethylene-alpha-olefin copolymer), thermoplastic elastomer, styrene analog thermoplastic elastomer particularly, as: styrene-butadiene-styrene multipolymer (SBS), hydrogenant styrene-butadiene-styrene multipolymer (SEBS), styrene-isoprene-styrene copolymer-(SIS), polyurethanes thermoplastic elastomer (polyester type or polyether-type).
The inorganic rare earth compound is rare earth oxide or the rare earth carbonate except the promethium.
Oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
Silane coupling agent is vinyltriethoxysilane (A151) or γ-An Bingjisanyiyangjiguiwan (KH550).
Tenderizer is a low molecular weight polyethylene wax, and synthetic softening agent is polytrimethylene adipate (PPA).
Used rare earth organic complex is acrylic rare earth salt, methacrylic acid rare-earth salts or their miscellany of 16 kinds of lanthanon except the promethium.Its preparation method can be represented with following reaction formula:
Wherein Re is a rare earth element, and HAA is acrylic or methacrylic acid.
Get a certain amount of rare earth oxide, add the deionized water of 2 times of rare earth oxide weight, add rare earth oxide molar weight (excessive) 1.5-2.5 vinylformic acid (or methacrylic acid) doubly, bathe heating, temperature is controlled at 60-90 ℃, stirring reaction 1-3 hour, filtered while hot, with the filtrate decompression distillation, steam and remove most of water and vinylformic acid, to there being crystal to occur, adding dehydrated alcohol cools off to such an extent that precipitate, be washed till neutrality with dehydrated alcohol, be dried to constant weight in 40 ℃ of left and right sides baking ovens, obtain product.
Material of the present invention can carry out processing and preparing on common equipments such as hot-rolling mill, Banbury mixer, twin screw extruder, processing temperature is controlled in the 100-260 ℃ of scope.Under the processing temperature condition,, add, add organic rare-earth ligand and inorganic rare earth compound again as Synergist S-421 95s such as oxidation inhibitor, tenderizer, silane coupling agents with the plastics fusion.Utilize the method moulding of rolling, extruding, injecting to get required X ray shielding matrix material.
The mishmetal content that rare earth modified leadless X-ray shielding plastic of the present invention adds is big, and has reached high dispersive and good interface consistency, makes the X ray shielding properties of material, mechanical property all reach the ideal effect.Can be widely used in projector and other protection of medical diagnosis X radial ray machine, X-ray diffractometer, electron microscope with the occasion staff of X ray generation.China's rare earth resources is abundant, and numerous in variety, therefore, rare earth modified leadless X-ray shielding plastic of the present invention has good application prospects.
Below in conjunction with embodiment effect of the present invention is described further.
Embodiment:
Embodiment 1:
The composition of each component and parts by weight are:
New LDPE (film grade) (LDPE) 100
Vinylformic acid europium 20
Neodymium trioxide 200
Gadolinium sesquioxide 100
Europium sesquioxide 200
KH550 3
Low molecular weight polyethylene wax 15
Antioxidant 1010 2
The preparation of shielding material: hot-rolling is warming up to 120 ℃, 100 parts of LDPE are added and make its fusion bag roller, add 2 parts of antioxidant 1010s, mixed 1 minute, and added 20 parts of vinylformic acid europiums again, add 200 parts of Neodymium trioxide, 100 parts of gadolinium sesquioxides and 200 parts of europium sesquioxides after being mixed in batches, mixed 10-20 minute, add 15 parts of low-molecular-weight wax then, mixed 1-2 minute, obtain rare earth modified leadless X-ray shielding plastic.
Embodiment 2:
The composition of each component and parts by weight are:
LDPE 100
Vinylformic acid europium 100
Vinylformic acid neodymium 50
Neodymium trioxide 200
Europium sesquioxide 200
KH550 2.5
Lower molecular weight PE wax 10
Antioxidant 1010 1.5
The preparation of shielding material: hot-rolling is warming up to 120 ℃, 100 parts of LDPE are added and make its fusion bag roller, add 2 parts of antioxidant 1010s, mixed 1 minute, and added 50 parts of 100 parts of vinylformic acid europiums and vinylformic acid neodymiums again, add 200 parts of Neodymium trioxide and 200 parts of europium sesquioxides after being mixed in batches, mixed 10-20 minute, add 10 parts of low-molecular-weight wax then, mixed 1-2 minute, obtain rare earth modified leadless X-ray shielding plastic.
Embodiment 3:
The composition of each component and parts by weight are:
Thermoplastic polyurethane (TPU) 100
Cerous carbonate 200
Vinylformic acid europium 50
Europium sesquioxide 200
Terbium sesquioxide 200
Polyester plasticizer (PPA) 8
Antioxidant 1010 1
KH550 1
Preparation method: hot-rolling is warming up to 160 ℃, add 100 parts of TPU plasticizing bag rollers, add 1 part of antioxidant 1010 again, add 100 parts of vinylformic acid samariums in batches, mixed 5-8 minute, add 50 parts of 200 parts of praseodymium carbonates, 100 parts of terbium sesquioxides and cerium oxide, simultaneously add 8 parts of PPA in batches, mixed 10-20 minute, add 1 part of KH550 then, mixed 1-2 minute, and obtained rare earth modified leadless X-ray shielding plastic.
Embodiment 4:
The composition of each component and parts by weight are:
Thermoplastic polyurethane (TPU) 50
Vinylformic acid samarium 50
Methacrylic acid cerium 50
Methacrylic acid praseodymium 50
Vinylformic acid terbium 50
Samarium trioxide 20
Polyester plasticizer (PPA) 2
Antioxidant 1010 1
KH550 2
Preparation method: hot-rolling is warming up to 160 ℃, add 50 parts of TPU plasticizing bag rollers, add 1 part of antioxidant 1010 again, add 50 parts of vinylformic acid samariums, 50 parts of methacrylic acid ceriums, 50 parts of methacrylic acid praseodymiums, 50 parts of vinylformic acid terbiums in batches, mixed 5-8 minute, add 20 parts of Samarium trioxides, simultaneously add 2 parts of PPA in batches, mixed 10-20 minute, add 2 parts of KH550 then, mixed 1-2 minute, and obtained rare earth modified leadless X-ray shielding plastic.
Embodiment 5:
The composition of each component and parts by weight are:
SBS 100
Vinylformic acid samarium 200
Methacrylic acid cerium 100
Methacrylic acid samarium 100
Vinylformic acid terbium 200
Samarium trioxide 200
Cerium oxide 200
Polyester plasticizer (PPA) 30
Antioxidant 1010 1.5
A151 2
Preparation method: hot-rolling is warming up to 160 ℃, add 100 parts of SBS plasticizing bag rollers, add 1.5 parts of antioxidant 1010s again, add 200 parts of vinylformic acid samariums, 100 parts of methacrylic acid ceriums, 100 parts of methacrylic acid praseodymiums, 200 parts of vinylformic acid terbiums in batches, mixed 5-8 minute, add 200 parts of 200 parts of Samarium trioxides and cerium oxide, simultaneously add 30 parts of PPA in batches, mixed 10-20 minute, add 1 part of A151 then, mixed 1-2 minute, and obtained rare earth modified leadless X-ray shielding plastic.
Embodiment 6:
The composition of each component and parts by weight are:
SEBS 100
Methacrylic acid terbium 200
Vinylformic acid samarium 200
Gadolinium sesquioxide 100
Europium sesquioxide 200
Polyester plasticizer (PPA) 10
Antioxidant 1010 2
A151 1
Preparation method: hot-rolling is warming up to 200 ℃, add 100 parts of SEBS plasticizing bag rollers, add 2 parts of antioxidant 1010s again, add 200 parts of methacrylic acid terbiums, 200 parts of vinylformic acid samariums in batches, mixed 5-8 minute, add 200 parts of 100 parts of gadolinium sesquioxides and europium sesquioxides, add simultaneously 10 parts of PPA in batches, mixed 10-20 minute, and added 1 part of A151 then, obtain rare earth modified leadless X-ray shielding plastic.
* represent the matrix material of unit thickness (mm) to be equivalent to the one-tenth-value thickness 1/10 of pure stereotype than protective value value in the table, it is good more that this is worth high more shielding properties.
Data in the table show, compare with plumbous elastomeric material, the shielding matrix material that with plastics is matrix has excellent X ray shielding properties, and its mechanical property is also fine, and in addition, material also has thermoplastic property, be easy to processing, can recycling, make shielding material can produce the product that makes new advances by the mode of reprocessing and come that this is very useful to economize on resources (particularly rare earth resources) at (even behind life-time service) after the use.
Claims (5)
1. rare earth modified leadless X-ray shielding plastic, it is formed and parts by weight are:
Plastics 50-100
Organic rare-earth ligand 20-600
Inorganic rare earth compound 20-600
Tenderizer 2-30
Oxidation inhibitor 1-3
Silane coupling agent 0.5-3
Said rare earth organic complex is acrylic rare earth salt, methacrylic acid rare-earth salts or their miscellany of 16 kinds of lanthanon except the promethium; The inorganic rare earth compound is rare earth oxide or the rare earth carbonate except the promethium.
2. according to the said rare earth modified leadless X-ray shielding plastic of claim 1, it is characterized in that: plastics are polyethylene, ethylene-alpha-olefin copolymer, styrene analog thermoplastic elastomer, polyester type or polyether(poly)urethane analog thermoplastic elastomer.
3. according to claim 1 or 2 said rare earth modified leadless X-ray shielding plastics, it is characterized in that: said tenderizer is low molecular weight polyethylene wax or polytrimethylene adipate.
4. according to claim 1 or 2 said rare earth modified leadless X-ray shielding plastics, it is characterized in that: silane coupling agent vinyl triethoxyl silane or γ-An Bingjisanyiyangjiguiwan.
5. according to claim 1 or 2 said rare earth modified leadless X-ray shielding plastics, it is characterized in that: oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
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| CNB2004100986106A CN1322047C (en) | 2004-12-14 | 2004-12-14 | Rare earth modified leadless X-ray shielding plastic |
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| CNB2004100986106A CN1322047C (en) | 2004-12-14 | 2004-12-14 | Rare earth modified leadless X-ray shielding plastic |
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|---|---|---|---|---|
| WO2010145082A1 (en) * | 2009-06-15 | 2010-12-23 | 北京化工大学 | Lead-free x-ray shielding rubber composite material |
| WO2010145081A1 (en) * | 2009-06-15 | 2010-12-23 | 北京化工大学 | Lead-free x-ray shielding plastic composite material |
| CN105131234A (en) * | 2015-09-08 | 2015-12-09 | 沈阳化工大学 | Radiation-resistant robot crawler and preparation method thereof |
| CN105399925A (en) * | 2015-12-02 | 2016-03-16 | 南京航空航天大学 | Fast-curing polyurethane-based gamma ray shielding composite material and preparation method thereof |
| CN105482225A (en) * | 2015-12-30 | 2016-04-13 | 上海师范大学 | Nuclear radiation prevention rare earth composite material and preparation method thereof |
| CN106633350A (en) * | 2016-12-12 | 2017-05-10 | 天津新霁科技有限公司 | Anti-radiation novel material and preparation method thereof |
| CN107910087A (en) * | 2017-01-18 | 2018-04-13 | 湖南康宁达医疗科技股份有限公司 | Radiation protection hard material and preparation method and application |
| CN108164858A (en) * | 2017-12-21 | 2018-06-15 | 宁波市河清源技术转移服务有限公司 | A kind of Th for adding radiation protection, Cr- combination ion exchange resins/nano oxidized aluminium composite material |
| CN109401279A (en) * | 2018-12-24 | 2019-03-01 | 李永强 | A kind of resin base shielding material |
| CN109849450A (en) * | 2018-12-29 | 2019-06-07 | 东华大学 | A kind of X-ray-preventing fabric and its preparation method and application with compared with highly-breathable |
| CN113004677A (en) * | 2021-01-29 | 2021-06-22 | 惠州市浩明科技股份有限公司 | High polymer material for protection and preparation method thereof |
| CN115403727A (en) * | 2021-05-28 | 2022-11-29 | 苏州科思迈新材料科技有限公司 | Polyurethane soft and hard segment adjustment and force-induced color change function integrated composite processing aid and preparation method thereof |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2028331C1 (en) * | 1991-12-11 | 1995-02-09 | Научно-производственное объединение "Композит" | Rubber mix |
| RU2000304C1 (en) * | 1992-04-06 | 1993-09-07 | Ермакова В.В., Загвоздкина О.В. | Rubber mixture for roentgen-protective material making |
| RU2054439C1 (en) * | 1992-10-30 | 1996-02-20 | Вера Филипповна Дебальчук | Rubber mixture for manufacturing of rubber being protection against x-rays |
| RU2066491C1 (en) * | 1994-02-25 | 1996-09-10 | Акционерное общество "Научно-исследовательский институт стали" | Material for protection against x-ray and gamma radiation |
| RU2156509C2 (en) * | 1997-02-11 | 2000-09-20 | Российский Федеральный Ядерный Центр - Всероссийский Научно-Исследовательский Институт Экспериментальной Физики | Laminated x-ray-protective material |
-
2004
- 2004-12-14 CN CNB2004100986106A patent/CN1322047C/en not_active Expired - Fee Related
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| WO2010145081A1 (en) * | 2009-06-15 | 2010-12-23 | 北京化工大学 | Lead-free x-ray shielding plastic composite material |
| CN101570606B (en) * | 2009-06-15 | 2011-01-05 | 北京化工大学 | Overall lead-free X-ray shielding rubber compound material |
| CN101572129B (en) * | 2009-06-15 | 2011-08-31 | 北京化工大学 | Overall lead-free X-ray shielding plastic compound material |
| US8728349B2 (en) | 2009-06-15 | 2014-05-20 | Beijing University Of Chemical Technology | Lead-free X-ray shielding rubber composite |
| WO2010145082A1 (en) * | 2009-06-15 | 2010-12-23 | 北京化工大学 | Lead-free x-ray shielding rubber composite material |
| CN105131234A (en) * | 2015-09-08 | 2015-12-09 | 沈阳化工大学 | Radiation-resistant robot crawler and preparation method thereof |
| CN105399925B (en) * | 2015-12-02 | 2018-12-14 | 南京航空航天大学 | It can rapid curing polyurethane gamma ray shielding composite material and preparation method |
| CN105399925A (en) * | 2015-12-02 | 2016-03-16 | 南京航空航天大学 | Fast-curing polyurethane-based gamma ray shielding composite material and preparation method thereof |
| CN105482225A (en) * | 2015-12-30 | 2016-04-13 | 上海师范大学 | Nuclear radiation prevention rare earth composite material and preparation method thereof |
| CN105482225B (en) * | 2015-12-30 | 2019-03-12 | 上海师范大学 | A kind of anti-nuclear radiation rare earth composite material and preparation method thereof |
| CN106633350A (en) * | 2016-12-12 | 2017-05-10 | 天津新霁科技有限公司 | Anti-radiation novel material and preparation method thereof |
| CN107910087A (en) * | 2017-01-18 | 2018-04-13 | 湖南康宁达医疗科技股份有限公司 | Radiation protection hard material and preparation method and application |
| CN108164858A (en) * | 2017-12-21 | 2018-06-15 | 宁波市河清源技术转移服务有限公司 | A kind of Th for adding radiation protection, Cr- combination ion exchange resins/nano oxidized aluminium composite material |
| CN109401279A (en) * | 2018-12-24 | 2019-03-01 | 李永强 | A kind of resin base shielding material |
| CN109849450A (en) * | 2018-12-29 | 2019-06-07 | 东华大学 | A kind of X-ray-preventing fabric and its preparation method and application with compared with highly-breathable |
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