CN101486809A - Preparation of rare-earth oxide / natural rubber composite material for X radiation protection - Google Patents
Preparation of rare-earth oxide / natural rubber composite material for X radiation protection Download PDFInfo
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- CN101486809A CN101486809A CNA2009100608497A CN200910060849A CN101486809A CN 101486809 A CN101486809 A CN 101486809A CN A2009100608497 A CNA2009100608497 A CN A2009100608497A CN 200910060849 A CN200910060849 A CN 200910060849A CN 101486809 A CN101486809 A CN 101486809A
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Abstract
The invention belongs to the field of medical X-ray protection materials and relates to a method for preparing rare earth oxide/caoutchouc composite materials that are used for X-ray protection. The method is characterized by including the following steps: 1) pretreatment of rare earth oxide; 2) selection of raw materials: selecting 100 parts of caoutchouc, 200-800 parts of pretreated rare earth oxide, 2-8 parts of zinc oxide, 0.2-1 part of stearic acid, 1-5 parts of sulfur, 0.5-4 parts of benzothiazole disulfide and 5-50 parts of softener according to parts by weight; and 3) the pretreated rare earth oxide, the caoutchouc, the zinc oxide, the stearci acid, the sulfur, the softener and the benzothiazole disulfide are sequentially added into internal mixer or an open mill, and mixing the materials for 5-60min under the blending temperature between 30-100 DEG C, thus obtaining the rare earth oxide/caoutchouc composite materials that are used for X-ray protection. The method has simple process and low production cost, and the prepared composite material is characterized by innocuity, light weight and strong ray absorption capacity.
Description
Technical field
The invention belongs to medical X-ray protection material field, especially relate to a kind of preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection.
Background technology
As everyone knows, in medical X-ray was checked, especially in interventional radiology program such as cardioangiography, angioplasty and delicate procedure, the medical worker must be exposed to for a long time in the X ray field and work.When the Long contact time X ray, can be to the sexual gland of human body, mammary gland, Red bone marrow etc. produce injury, also can cause diseases such as leukemia, bone tumor if surpass certain dosage, bring serious threat to life.At present, the X-ray proof material overwhelming majority is to make the rubber plate of filler with lead, plumbous oxide or other lead salt both at home and abroad, or the lead foil that is covered by polymeric film is formed by stacking.Adopt these protective materials, not only heavy, and lead element wherein also has certain toxicity, can cause to a certain degree pollution to environment.Simultaneously, because filler content is very high in the rubber plate, perhaps because lead foil repeatedly may rupture after the repeated flex, material is not very durable, and this material flexibility is poor, is difficult to be processed into required model.
Canadian Martin J.Yaffe in 1991, U.S. Paul H.Murphy studied the X-ray-preventing matrix material of compositions such as plumbous and barium, tungsten tin, copper in 1993, though prepared X-ray-preventing material is lighter than traditional leaded X-ray-preventing material, and the also bigger improvement of the physical and mechanical properties of its ray absorption properties and material, but this matrix material weight is still heavier, and cost is higher, thereby has limited its application and popularization.Tilak M.Shah people such as (US 5,245,195) invented a kind of comparatively novel X-ray-preventing material in 1993, reached the purpose that absorbs ray by add barium sulfate in thermoplastic elastomer.Its advantage is nontoxic, cleans easily and sterilizes, and still can keep the better physical mechanical property when filler content is higher, but because barium element institute's weight percent low excessively (59%) in this compound is unfavorable for the reduction of X-ray-preventing material weight.
China Zhang Qixin people such as (CN1073263C) has invented a kind of lanthanon composite shielding material that is used for mixing containing of medical X-ray protection, its advantage is that ray absorption capacity is strong, in light weight and cost is low, but because composite shielding material contains a certain amount of lead in forming, thereby, can cause to a certain degree pollution to environment.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection, this method technology is simple, production cost is low, and prepared matrix material has the characteristics nontoxic, in light weight, that ray absorption capacity is strong.
To achieve these goals, technical scheme of the present invention is: be used for the preparation method of the rare-earth oxide/natural rubber composite material of X-ray protection, it is characterized in that it comprises the steps:
1) pre-treatment of rare earth oxide: be by the shared parts by weight of each raw material: 100 parts of rare earth oxides, 1～5 part of coupling agent, choose rare earth oxide and coupling agent; Rare earth oxide and coupling agent are placed high-speed mixer, so that (1200～1500r/min) stir 10～30min, get pretreated rare earth oxide, standby at a high speed;
2) choosing of raw material: be: 100 parts of natural rubbers, 200～800 parts of pretreated rare earth oxides, 2～8 parts in zinc oxide, 0.2～1 part of stearic acid, 1～5 part in sulphur, 0.5～4 part of benzothiazyl disulfide, 5～50 parts of tenderizers by the shared parts by weight of each raw material, choose natural rubber, pretreated rare earth oxide, zinc oxide, stearic acid, sulphur, benzothiazyl disulfide and tenderizer, standby;
3) in Banbury mixer or mill, add pretreated rare earth oxide, natural rubber, zinc oxide, stearic acid, sulphur (vulcanizing agent), tenderizer and benzothiazyl disulfide successively, under 30～100 ℃ blending temperature, mixing 5～60 minutes, obtain a rubber unvulcanizate; Then rubber unvulcanizate was vulcanized 30 minutes down at 140 ℃, must be used for the rare-earth oxide/natural rubber composite material of X-ray protection.
The described rare earth oxide of step 1) is the single rare earth oxide compound, and concrete chemical formula is: R
2O
3, wherein R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc; Perhaps described rare earth oxide is that concrete chemical formula is: R
2O
3The single rare earth oxide compound in any mixture that (contains any two kinds) more than two kinds, be any proportioning between each single rare earth oxide compound in the mixture; The purity of described rare earth oxide is greater than 99.5% (quality), and grain diameter is 0.3-4 μ m, and the rare-earth oxidation raw material can be commercially available rare earth oxide.
Described coupling agent is a titanate coupling agent, is the NTC-201 of double-gate chemical plant, Nanjing production.
Described tenderizer is a phthalate, mainly contains dimixo-octyl phthalate (DOP) or dibutyl phthalate (DBP).
The invention has the beneficial effects as follows:
1, because the polarity of rare earth oxide and natural rubber is different, before the rare earth oxide filling natural rubber, rare earth oxide must use coupling agent treatment, to increase the interaction of itself and natural rubber, impel rare earth oxide to be evenly dispersed in the natural rubber, improve the mechanical property of matrix material; The present invention is filled into rare earth oxide in the natural rubber, has obtained a kind of rare-earth oxide/natural rubber composite material that is used for X-ray protection.Owing to adopt lead, so the present invention has nontoxic characteristics.
2, traditional leaded X-ray-preventing material is higher than 88keV and the ray between 13-40keV has good particle receptivity for energy, but but very weak to the particle receptivity of the ray outside this scope.And the medical X-ray energy that is produced by the following tube voltage of 130KVp usually is lower than 88keV, and the power spectrum peak of most X-rays is in the energy area of 40-88keV, therefore, be conspicuous with lead as its defective of absorbing material that absorbs medical X-ray.And rare earth element K layer ABSORPTION EDGE is between 40-88keV, strong to the X-ray absorption capacity, simultaneously the ordination number of rare earth element is less than the ordination number of lead, thereby for the weight of the rare earth oxide of the equal volume weight less than lead, helps the reduction of X-ray-preventing material weight.The simple leaded X-ray-preventing material of the weight ratio of rare-earth oxide/natural rubber composite material of the present invention light by 20～40% (weight).
3, this method technology is simple, production cost is low.China's rare earth resources is abundant, ore reserve is distant to rank first in the world, and therefore, the develop and spread rare earth is used not only to making full use of the rich rare earth resources of China, the development that promotes the rare earth industry has great importance, and helps cultivating the new industry of advantage with Chinese characteristics.Used rare earth oxide can be the close rare earth oxide mixture of single rare earth oxide compound or chemical property among the present invention.Thereby avoided difficult rare earth oxide chemical separation program, and saved expensive separation cost, reduced production cost widely.
4, add flowing property and the processing characteristics that tenderizer helps improving rare-earth oxide/natural rubber composite material among the present invention, make rare-earth oxide/natural rubber composite material have certain flexibility.
5, this method technology is simple, production cost is low.
The rare-earth oxide/natural rubber composite material that is used for X-ray protection that the present invention makes is suitable for making clothes, jacket, apron, robe, gloves, Tiroidina protector, sexual gland protector, patient protection clothes and curtain, sack etc.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Be used for the preparation method of the rare-earth oxide/natural rubber composite material of X-ray protection, it comprises the steps:
1) pre-treatment of rare earth oxide: be by the shared parts by weight of each raw material: 100 parts of rare earth oxides, 3 parts of coupling agents, choose rare earth oxide and coupling agent; Rare earth oxide and coupling agent are placed high-speed mixer,, get pretreated rare earth oxide with 1200r/min high-speed stirring 10min, standby; Described coupling agent is a titanate coupling agent, is the NTC-201 of double-gate chemical plant, Nanjing production;
Described rare earth oxide is the single rare earth oxide compound, lanthanum trioxide (La
2O
3).
2) choosing of raw material: press the prescription in the table 1, choose natural rubber, pretreated rare earth oxide, zinc oxide, stearic acid, sulphur, benzothiazyl disulfide (altax) and tenderizer, standby; Described tenderizer is dimixo-octyl phthalate (DOP);
3) in Banbury mixer, add pretreated rare earth oxide, natural rubber, zinc oxide, stearic acid, sulphur (vulcanizing agent), tenderizer and benzothiazyl disulfide successively, under 50～60 ℃ blending temperature, mixing 15 minutes, obtain a rubber unvulcanizate; Then rubber unvulcanizate was vulcanized 30 minutes down at 140 ℃, make the rare-earth oxide/natural rubber composite material that is used for X-ray protection.For the performance to material is tested, the gained rubber unvulcanizate can be become the thick sample of 2mm with the vulcanizing press molded vulcanization.The hardness of sample is by standard GB/T531 test; Tensile strength and tensile yield are tested according to standard GB/T528.
Embodiment 2:
Substantially the same manner as Example 1, difference is: used rare earth oxide is a mixture (lanthanum trioxide and cerium oxide), wherein lanthanum trioxide (La
2O
3) and cerium oxide (Ce
2O
3) weight respectively accounts for 50%, and rare earth oxide is different with the natural rubber proportioning, sees Table 1.
Embodiment 3:
Substantially the same manner as Example 1, it is the single rare earth oxide compound that difference is used, europium sesquioxide (Eu
2O
3), commercially available.And rare earth oxide is different with the natural rubber proportioning, sees Table 1.
The protective value test condition: x-ray tube voltage 100kV, half-value layer 0.16mmCu, the protective value of each sample is the mean value of three different sites measurement results.
The X ray absorption rate testing: the inherent filtration of X-ray production apparatus is 2mmAl, and the specific absorption of each sample is the mean value of three different sites measurement results.
X ray specific absorption=(1-sees through the air kerma rate/incident air kerma rate of sample) * 100%.
The test result of embodiment 1～3 as shown in Table 1 and Table 2.From the gained result, the prepared rare-earth oxide/natural rubber composite material that is used for X-ray protection of the present invention not only has excellent shielding properties, also has the good mechanical performance simultaneously.By changing system formulation, can satisfy the needs of the various clothes of X-ray-preventing that different protective values require, and production cost is starkly lower than similar products at home and abroad, have better market application.
Table 1
Table 2
Embodiment 4:
Be used for the preparation method of the rare-earth oxide/natural rubber composite material of X-ray protection, it comprises the steps:
1) pre-treatment of rare earth oxide: be by the shared parts by weight of each raw material: 100 parts of rare earth oxides, 1 part of coupling agent, choose rare earth oxide and coupling agent; Rare earth oxide and coupling agent are placed high-speed mixer,, get pretreated rare earth oxide with 1500r/min high-speed stirring 10min, standby;
Described rare earth oxide is a mixture (cerium oxide, Praseodymium trioxide and Erbium trioxide), wherein cerium oxide (Ce
2O
3) weight accounts for 20%, Praseodymium trioxide (Pr
2O
3) weight accounts for 50%, Erbium trioxide (Er
2O
3) weight accounts for 30%, and is commercially available; Grain diameter is 0.3-4 μ m.Coupling agent is a titanate coupling agent, is the NTC-201 of double-gate chemical plant, Nanjing production;
2) choosing of raw material: be: 100 parts of natural rubbers, 200 parts of pretreated rare earth oxides, 2 parts in zinc oxide, 0.2 part of stearic acid, 1 part in sulphur, 0.5 part of benzothiazyl disulfide (altax), 5 parts of tenderizers by the shared parts by weight of each raw material, choose natural rubber, pretreated rare earth oxide, zinc oxide, stearic acid, sulphur, benzothiazyl disulfide (altax) and tenderizer, standby; Described tenderizer is dibutyl phthalate (DBP);
3) in Banbury mixer, add pretreated rare earth oxide, natural rubber, zinc oxide, stearic acid, sulphur (vulcanizing agent), tenderizer and benzothiazyl disulfide successively, under 30 ℃ blending temperature, mixing 60 minutes, must be used for the rare-earth oxide/natural rubber composite material of X-ray protection.
Embodiment 5:
Be used for the preparation method of the rare-earth oxide/natural rubber composite material of X-ray protection, it comprises the steps:
1) pre-treatment of rare earth oxide: be by the shared parts by weight of each raw material: 100 parts of rare earth oxides, 5 parts of coupling agents, choose rare earth oxide and coupling agent; Rare earth oxide and coupling agent are placed high-speed mixer,, get pretreated rare earth oxide with 1300r/min high-speed stirring 10min, standby;
Described rare earth oxide is a mixture (europium sesquioxide, Praseodymium trioxide and ytterbium oxide), wherein europium sesquioxide (Eu
2O
3) weight accounts for 30%, Praseodymium trioxide (Pr
2O
3) weight accounts for 30%, ytterbium oxide (Yb
2O
3) weight accounts for 40%; Grain diameter is 0.3-4 μ m.Described coupling agent is a titanate coupling agent, is the NTC-201 of double-gate chemical plant, Nanjing production;
2) choosing of raw material: be: 100 parts of natural rubbers, 800 parts of pretreated rare earth oxides, 8 parts in zinc oxide, 1 part of stearic acid, 5 parts in sulphur, 4 parts of benzothiazyl disulfides (altax), 50 parts of tenderizers by the shared parts by weight of each raw material, choose natural rubber, pretreated rare earth oxide, zinc oxide, stearic acid, sulphur, benzothiazyl disulfide (altax) and tenderizer, standby; Described tenderizer is dimixo-octyl phthalate (DOP);
3) in mill, add pretreated rare earth oxide, natural rubber, zinc oxide, stearic acid, sulphur (vulcanizing agent), tenderizer and benzothiazyl disulfide successively, under 100 ℃ blending temperature, mixing 5 minutes, must be used for the rare-earth oxide/natural rubber composite material of X-ray protection.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention, the bound value and the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (4)
1. the preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection is characterized in that it comprises the steps:
1) pre-treatment of rare earth oxide: be by the shared parts by weight of each raw material: 100 parts of rare earth oxides, 1～5 part of coupling agent, choose rare earth oxide and coupling agent; Rare earth oxide and coupling agent are placed high-speed mixer,, get pretreated rare earth oxide with high-speed stirring 10～30min of 1200～1500r/min, standby;
2) choosing of raw material: be: 100 parts of natural rubbers, 200～800 parts of pretreated rare earth oxides, 2～8 parts in zinc oxide, 0.2～1 part of stearic acid, 1～5 part in sulphur, 0.5～4 part of benzothiazyl disulfide, 5～50 parts of tenderizers by the shared parts by weight of each raw material, choose natural rubber, pretreated rare earth oxide, zinc oxide, stearic acid, sulphur, benzothiazyl disulfide and tenderizer, standby;
3) in Banbury mixer or mill, add pretreated rare earth oxide, natural rubber, zinc oxide, stearic acid, sulphur, tenderizer and benzothiazyl disulfide successively, under 30～100 ℃ blending temperature, mixing 5～60 minutes, obtain a rubber unvulcanizate; Then rubber unvulcanizate was vulcanized 30 minutes down at 140 ℃, must be used for the rare-earth oxide/natural rubber composite material of X-ray protection.
2. the preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection according to claim 1 is characterized in that: the described rare earth oxide of step 1) is the single rare earth oxide compound, and concrete chemical formula is: R
2O
3, wherein R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc; Perhaps described rare earth oxide is that concrete chemical formula is: R
2O
3The single rare earth oxide compound in any mixture more than two kinds, be any proportioning between each single rare earth oxide compound in the mixture.
3. the preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection according to claim 1 is characterized in that: described coupling agent is a titanate coupling agent, is the NTC-201 of double-gate chemical plant, Nanjing production.
4. the preparation method who is used for the rare-earth oxide/natural rubber composite material of X-ray protection according to claim 1 is characterized in that: described tenderizer is a phthalate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974181A (en) * | 2010-11-17 | 2011-02-16 | 武汉工程大学 | Method for preparing rare-earth oxide/rubber composite material for low-frequency sound absorption |
| CN104045868A (en) * | 2014-06-16 | 2014-09-17 | 中国热带农业科学院农产品加工研究所 | Preparation method of nano cerium oxide/natural rubber composite material |
| CN104403145A (en) * | 2014-11-10 | 2015-03-11 | 苏州蔻美新材料有限公司 | Medical X-ray preventing glove and preparation method thereof |
| CN105949723A (en) * | 2016-05-24 | 2016-09-21 | 北京航空航天大学 | Ionizing-radiation-preventive composite material and preparation method thereof |
| CN106751943A (en) * | 2016-12-12 | 2017-05-31 | 天津新霁科技有限公司 | A kind of radiation proof foldable type new material and preparation method thereof |
| CN109836710A (en) * | 2019-04-15 | 2019-06-04 | 广州新莱福磁材有限公司 | Super soft X/ gamma-rays protective materials of one kind and preparation method thereof |
-
2009
- 2009-02-24 CN CN2009100608497A patent/CN101486809B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974181A (en) * | 2010-11-17 | 2011-02-16 | 武汉工程大学 | Method for preparing rare-earth oxide/rubber composite material for low-frequency sound absorption |
| CN101974181B (en) * | 2010-11-17 | 2013-07-10 | 武汉工程大学 | Method for preparing rare-earth oxide/rubber composite material for low-frequency sound absorption |
| CN104045868A (en) * | 2014-06-16 | 2014-09-17 | 中国热带农业科学院农产品加工研究所 | Preparation method of nano cerium oxide/natural rubber composite material |
| CN104403145A (en) * | 2014-11-10 | 2015-03-11 | 苏州蔻美新材料有限公司 | Medical X-ray preventing glove and preparation method thereof |
| CN105949723A (en) * | 2016-05-24 | 2016-09-21 | 北京航空航天大学 | Ionizing-radiation-preventive composite material and preparation method thereof |
| CN106751943A (en) * | 2016-12-12 | 2017-05-31 | 天津新霁科技有限公司 | A kind of radiation proof foldable type new material and preparation method thereof |
| CN109836710A (en) * | 2019-04-15 | 2019-06-04 | 广州新莱福磁材有限公司 | Super soft X/ gamma-rays protective materials of one kind and preparation method thereof |
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Assignee: Hubei Nuoke Pharmaceutical Co., Ltd. Assignor: Wuhan Institute of Technology Contract record no.: 2011420000163 Denomination of invention: Preparation of rare-earth oxide / natural rubber composite material for X radiation protection Granted publication date: 20110504 License type: Exclusive License Open date: 20090722 Record date: 20110707 |
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