CN106674663A - Environmental-protection type X-ray protection styrene butadiene rubber composition and preparation method thereof - Google Patents
Environmental-protection type X-ray protection styrene butadiene rubber composition and preparation method thereof Download PDFInfo
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- CN106674663A CN106674663A CN201610948545.4A CN201610948545A CN106674663A CN 106674663 A CN106674663 A CN 106674663A CN 201610948545 A CN201610948545 A CN 201610948545A CN 106674663 A CN106674663 A CN 106674663A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention provides an environmental-protection type X-ray protection rare earth oxide/styrene butadiene rubber composition, which mainly comprises: 1) 100% styrene butadiene rubber latex (dried rubber) and (2) 200-400% of an organized rare earth oxide. According to the present invention, the surface of a rare earth oxide is subjected to acid esterification treatment with a surfactant aliphatic diisocyanate, isolation is performed with an amide-based water-soluble polymer, a styrene butadiene rubber latex is subjected to acylation treatment with an acid anhydride to warp the surface so as to organize the surface of the rare earth oxide particles, and finally direct mixing with the styrene butadiene rubber latex without any additive, agglomeration, dehydration and drying are performed to prepare the environmental-protection type rare earth oxide/styrene butadiene rubber composition; and the composition has characteristics of high rare earth oxide filling amount, uniform rare earth oxide dispersing, excellent X-ray shielding performance, light weight compared to the conventional lead-containing X-ray prevention material, environment protection, no pollution and the like. The present invention further discloses a preparation method of the composition.
Description
Technical field
The present invention relates to protect butadiene-styrene rubber composition of X-ray and preparation method thereof, and in particular to one kind is without lead screen X-ray
Rare earth oxide/butadiene-styrene rubber composition and preparation method thereof.
Background technology
It is well known that as the continuous development of petrochemical technology, increasing equipment or part need to carry out Non-Destructive Testing, and
Ray detection is the important component part of Non-Destructive Testing.Especially in X-ray detection, worker must for a long time be exposed to X and penetrate
In the field of line, injury can be produced to the sexual gland of human body, mammary gland, red marrow etc., if can also cause leukaemia, bone more than certain dosage
The diseases such as tumour, seriously threaten to life zone.At present, domestic and international X-ray-preventing material be mostly with lead, lead oxide or its
Its lead salt makees the rubber slab of filler, or the lead foil covered by thin polymer film is formed by stacking.It is not only stupid using these protective materials
Weight, and lead element therein also has certain toxicity, and a certain degree of pollution can be caused to environment.Simultaneously as rubber slab
Interior filer content is very high, or may rupture because lead foil is repeated several times after bending, it is difficult to be processed into nonstandard special-shaped structure piece
Meet actually detected requirement, therefore the environment-friendly type macromolecule material without lead screen X-ray becomes the important of materialogy research field
Problem, has carried out to this studied in large quantities both at home and abroad.
In prior art, the research of relevant environment-friendly type lead-free shielding X-ray mainly uses non-lead heavy metal or other are not contained
Some auxiliary agents are added in the compound of lead, after stirring by traditional banburying and mixed refining process mode elastomeric material is filled into
Method preparing.Such as：Us 245195 provides a kind of addition barium sulfate in thermoplastic elastomer (TPE) and reaches and absorbs the anti-of ray
X-ray material.CN1073263C provides a kind of for medical X-ray protection bright-coloured series elements composite shielding material containing mixing.
ZL200910060849.7 provides a kind of using adding titanate coupling agent to pre-process rare earth oxide, then in banburying
Rare-earth oxide/natural rubber composite material for X-ray protection is mixed with out with natural rubber in machine or mill
Method.ZL200910059052.5 provides a kind of rubber-base flexible shielding material and its preparation technology.The shielding material is with resistance to spoke
Improve its hardness and toughness according to based on butadiene-styrene rubber and by additive, Jing virgin rubbers are plasticated, banburying (or mill), oxidation are handed over
Connection processing technology production, with calendering process by boron carbide powder even dispersion in butadiene-styrene rubber matrix.Although said method is substantially
The protection to X-ray is improve, but these methods still suffer from certain limitation, because unleaded shielding material belongs to inorganic material
And particle diameter is little, specific surface is big, surface energy is high, easily reunite, the poor compatibility with elastomeric material, only by coupling agent treatment and
Traditional banburying, the processing mode of mixing are difficult to dispersed in elastomeric material, so not only can affect to protect X to penetrate
The effect of line, but also the performance of elastomeric material can be damaged.
The content of the invention
Present invention aim at providing a kind of rare earth oxide/butadiene-styrene rubber composition of protection X-ray.The invention initially with
Surfactant aliphatic diisocyanate carries out Esterification process to rare earth oxide surface, water-soluble followed by amide-type
Macromolecule is isolated, and then carries out being acylated process to styrene-butadiene latex to its Surface coating using acid anhydrides, finally any need not be added
Plus agent directly mixes with styrene-butadiene latex, condenses, being dehydrated, being dried to prepare environment-friendly type rare earth oxide/butadiene-styrene rubber composition.This
The method of kind not only solves rare earth oxide and the little problem of addition is caused because of reunion, but also improves rare earth oxide and fourth
Benzene rubber compatibility, it is ensured that rare earth oxide particle can be evenly dispersed into butadiene-styrene rubber body matrix, it is ensured that had to X-ray
Structure adaptability in very strong shielding and actual application.Present invention further propose that the preparation method of said composition.
" part " of the present invention each means mass parts.
A kind of rare earth oxide/butadiene-styrene rubber composition for X-ray protection of the present invention, it is dry with styrene butadiene rubber latex
The quality of glue is absolutely meter, mainly including following component：
(1) styrene butadiene rubber latex (dry glue) 100%
(2) organise rare earth oxide 200~400%
Wherein, the described rare earth oxide that organises is to rare-earth oxidation initially with surfactant aliphatic diisocyanate
Thing surface carries out Esterification process, is then isolated using amide-type water soluble polymer, then using acid anhydrides in catalyst
In the presence of acylation reaction is carried out to styrene butadiene rubber latex, subsequently its particle surface cladding is processed to prepare.Rare earth oxide
Selected from single rare earth oxide, concrete chemical formula is：RxOy, wherein R be La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu, Y and Sc；Or the mixture of any two or the two kinds of any of the above proportionings in single rare earth oxide；Institute
The purity of rare earth oxide is stated more than 99.5%, grain diameter is 0.1~5 μm.The surfactant is the isocyanide of aliphatic two
Acid esters, selected from hexamethylene diisocyanate (HDI), IPDI (IPDI), dicyclohexyl methyl hydride -4,4 ' one
One kind in diisocyanate (MDI), methylcyclohexane diisocyanate (HTDI), preferred HTDI.The amide-type is water-soluble
Macromolecule is the polymer that polyolefin is backbone structure, selected from polyacrylamide, polyacrylic acid, polymethylacrylic acid, poly- methyl
One kind in hydroxy-ethyl acrylate, polyhexene acid amides, preferred poly amic acid, its consumption is 3%~10%.Described acid anhydrides is
Dibasic acid anhydride compound, one kind in maleic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride is preferred adjacent
Phthalate anhydride.The catalyst is selected from aluminum trichloride (anhydrous) (AlCl3), boron trifluoride (BF3), butter of tin (SnCl4), two
Zinc chloride (ZnCl2) in one kind, preferred AlCl3, its addition is 0.05~0.3 part, preferably 0.08~0.25 part.
Styrene butadiene rubber latex of the present invention is by breast by conjugated diene hydrocarbon compound and aryl ethylene class compound
Liquid polymerization copolymerization is formed.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound is benzene second
One kind in alkene, AMS, 2- propenyl benzenes, ethyl styrene and their derivative.Wherein styrene butadiene rubber latex
Solid content 20~45%, combinated styrene content content 15~25%, 50~200nm of latex particle size.
The preparation of rubber composition of the present invention is carried out in condensing field, and specific preparation process comprises the steps：
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：In terms of the mass parts of styrene-butadiene latex (dry glue), 100 parts of butylbenzene are initially charged in polymeric kettle
Latex, 1~5 part of emulsifying agent, 5~10 parts of solvents, stirring, heating, when kettle temperature degree to be polymerized reaches 25~50 DEG C, in stirring condition
Under be rapidly added 0.05~0.3 part of catalyst, when system becomes orange red add 9~15 parts of acid anhydrides, stirring reaction 1~
4h, adds the diluted hydrochloric acid aqueous solution terminating reaction that 10~15 powder mass concentrations are 1.5%~5.0%, suction filtration, washing to be obtained and be acylated
Styrene-butadiene latex (degree of acetylation of styrene-butadiene latex is 5%~10%).
B organises the preparation of rare earth oxide：Based on the mass parts of rare earth oxide, take 100 parts of rare earth oxides and 5.0~
10.0 parts of surfactants, 300~500 parts of deionized waters are added in polymeric kettle, stirring 10~30min of mixing；It is subsequently added 3
~10 parts of amide-type water soluble polymers, stirring 10~30min of mixing, is 9~12 with buffer regulation system pH value；Then plus
Enter 5~10 parts of emulsifying agents and 10~30 parts of acylated styrene-butadiene latexes, stirring is warming up to 50~90 DEG C, after 3~5hr of stirring reaction, Jing
Washing, dehydration, dry, grinding are obtained the rare earth oxide that organises.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex (dry glue), 100 are taken
Part styrene-butadiene latex (dry glue) and 5~10 parts of emulsifying agents, 300~600 parts of deionized waters be added to stirring in condensing field mix 10~
30min, is subsequently adding 200~400 parts of rare earth oxides that organise, and is 9~12 with buffer regulation system pH value, is warming up to 60
When~90 DEG C, stirring 1~3hr of mixing is subsequently adding 3~6 parts of flocculating agents and is condensed, last scrubbed, dehydration, dry, pressure
Block is obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.
The present invention can be using conven-tional adjuvants generally in the art to emulsifying agent, buffer, flocculating agent for being adopted etc., and it adds
It is also that those skilled in the art can be with calculated conventional amount used according to the consumption of latex to enter amount, and the present invention does not do special limit
It is fixed.As described in the present invention emulsifying agent is known to those skilled in the art, can be anion emulsifier and non-ionic emulsifier
One or more in agent.Such as：Selected from fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate, poly-
The mixture of one or more in oxygen ethene sorbitan monooleate, preferred neopelex.
The one kind of buffer of the present invention in sodium carbonate, sodium acid carbonate, NaOH, ammoniacal liquor, ammonium hydrogen carbonate, preferred hydrogen
Sodium oxide molybdena.
Cohesion of the present invention, poly- using acid cure, the technology is general for those skilled in the art, and described flocculating agent is usual
For inorganic acid, such as one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
Rare earth oxide/butadiene-styrene rubber composition of a kind of environment-friendly type protection X-ray of the present invention and preparation method thereof.This
Invention is carried out under aqueous basic conditions initially with surfactant aliphatic diisocyanate to rare earth oxide surface
It is Esterification, be subsequently added polyolefin base class acid amides and end-blocking effect played to cyanic acid ester group, prevent the mutual self-priming of diisocyanate and
Cause the adhesion of particle, be so greatly enhanced the loading of rare earth oxide, the effect for preferably shielding X-ray can be reached
Really.Produce with the cyanic acid ester group of rare earth oxide particle surface finally by the polar group amide groups in acylated styrene-butadiene latex
" hydrogen bond action ", rare earth oxide particle surface can be formed securely, close styrene-butadiene latex clad, realize rare earth oxygen
Compound particle surface organises.Nonpolar and phenyl ring design feature can significantly reduce particle surface in styrene-butadiene latex molecule
Activation energy, hinder particle between mutual reunion, the rare earth oxide particle of big loading can be realized with single particle
Form stable ground is present.
Simultaneously because styrene-butadiene latex clad so that organising has good phase between rare earth oxide and styrene-butadiene latex matrix
Capacitive, then any surfactant need not be added can be realized as rare earth oxide particle equably dividing in styrene-butadiene latex
Dissipate so that rare earth oxide is given full play to the shield effectiveness of X-ray under micron order peptizaiton, so as to be shielded
Environment-friendly type rare earth oxide/butadiene-styrene rubber the composition of function admirable.Said composition has excellent X-ray shield performance, ratio
Traditional leaded X-ray-preventing material is light, it is environment friendly and pollution-free the features such as.
In addition, in the preparation process of the butadiene-styrene rubber composition without lead screen X-ray, rare earth oxide particle is not through opening
Mill and banbury carry out traditional mixing and banburying to process, but directly prepare with styrene-butadiene latex blending, cohesion.So keep away
The problems such as having exempted from skidding, incipient scorch, the uneven dispersion of sizing material work in-process appearance.Its preparation method is simple, and waste material is few, without dirt
Dye, suitable industrialized production.
Specific embodiment
Enumerate following examples and comparative example to illustrate the invention effect of the present invention, but protection scope of the present invention and not only limit
In these embodiments and comparative example." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
(2) analysis test method：
The measure of degree of acetylation：Tested using Japanese Shimadzu IR-460 type infrared spectrometer.
300% stress at definite elongation：Method in execution standard GB/T8656-1998.
Elongation at break：Method in execution standard GB/T1040-1992.
Lead equivalent test condition：X-ray tube voltage 120kV, half-value layer 0.16mmCu, the lead equivalent of each sample is three differences
The mean value of Site Determination result.
X-ray absorption rate is tested：X-ray tube voltage 100kV, inherent filtration is 2mmAL, the absorptivity of each sample be three not
With the mean value of Site Determination result.
Embodiment 1
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：100 parts of styrene-butadiene latex SBR1500,1.0 parts of detergent alkylates are initially charged in polymeric kettle
Sodium sulfonate, 5 parts of CS2, stirring, heating, when kettle temperature degree to be polymerized reaches 30 DEG C, be rapidly added under agitation 0.08 part it is anhydrous
Alchlor, adds 9 parts of phthalic anhydrides, stirring reaction 1.0h to add 10 parts of quality dense when system becomes orange red
Spend the diluted hydrochloric acid aqueous solution terminating reaction for 2.0%, suction filtration, washing are obtained acylated styrene-butadiene latex SBR1500 (degree of acetylation is
5.5%).
B organises the preparation of rare earth oxide：Take 100 parts of rare earth oxide (La2O3、CeO2And Pr2O3Mixture) and 5.0 parts
HTDI, 300 parts of deionized waters are added in polymeric kettle, stirring mixing 10min；It is subsequently added 3 parts of polyacrylamides, stirring mixing
10min, is 10 with buffer regulation system pH value；It is subsequently adding 5 parts of neopelexes and 10 parts of acylated styrene-butadiene latexes
SBR1500 (degree of acetylation is 5.5%), stirring is warming up to 60 DEG C, after stirring reaction 3.0hr, scrubbed, dehydration, dry, grinding
The rare earth oxide that organises is obtained.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 5
Part neopelex, 300 parts of deionized waters are added to stirring mixing 10min in condensing field, be subsequently adding 200 parts it is organic
Change rare earth oxide, be 10 with buffer regulation system pH value, when being warming up to 60 DEG C, stirring mixing 1.0hr is subsequently adding 3 parts
Hydrochloric acid is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.Take
Sample is analyzed：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Embodiment 2
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：With embodiment 1.
B organises the preparation of rare earth oxide：With embodiment 1.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 6
Part neopelex, 400 parts of deionized waters are added to stirring mixing 15min in condensing field, be subsequently adding 260 parts it is organic
Change rare earth oxide, be 11 with buffer regulation system pH value, when being warming up to 70 DEG C, stirring mixing 1.5hr is subsequently adding 4 parts
Hydrochloric acid is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.Take
Sample is analyzed：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Embodiment 3
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：100 parts of styrene-butadiene latex SBR1500,3.0 parts of detergent alkylates are initially charged in polymeric kettle
Sodium sulfonate, 8 parts of CS2, stirring, heating, when kettle temperature degree to be polymerized reaches 40 DEG C, be rapidly added under agitation 0.17 part it is anhydrous
Alchlor, adds 12 parts of phthalic anhydrides, stirring reaction 3.0hr to add 12 parts of quality when system becomes orange red
Concentration is 3.0% diluted hydrochloric acid aqueous solution terminating reaction, and suction filtration, washing are obtained acylated styrene-butadiene latex SBR1500 (degree of acetylation is
8.1%).
B organises the preparation of rare earth oxide：Take 100 parts of rare earth oxide (La2O3、CeO2And Pr2O3Mixture) and 8.5 parts
HTDI, 400 parts of deionized waters are added in polymeric kettle, stirring mixing 20min；It is subsequently added 8 parts of polyacrylamides, stirring mixing
20min, is 11 with buffer regulation system pH value；It is subsequently adding 7 parts of neopelexes and 25 parts of acylated styrene-butadiene latexes
SBR1500 (degree of acetylation is 8.1%), stirring is warming up to 80 DEG C, after stirring reaction 4.0hr, scrubbed, dehydration, dry, grinding
The rare earth oxide that organises is obtained.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 8
Part neopelex, 500 parts of deionized waters are added to stirring mixing 20min in condensing field, be subsequently adding 300 parts it is organic
Change rare earth oxide, be 11 with buffer regulation system pH value, when being warming up to 80 DEG C, stirring mixing 2.0hr is subsequently adding 5 parts
Hydrochloric acid is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.Take
Sample is analyzed：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Embodiment 4
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：With embodiment 3.
B organises the preparation of rare earth oxide：With embodiment 3.
(2) preparation of rare earth oxide/butadiene-styrene rubber composition：Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 9 part 12
Sodium alkyl benzene sulfonate, 550 parts of deionized waters are added to stirring mixing 25min in condensing field, are subsequently adding 320 parts of rare earths that organise
Oxide, is 11 with buffer regulation system pH value, and when being warming up to 85 DEG C, stirring mixing 2.5hr is subsequently adding 5.5 parts of hydrochloric acid
It is condensed, last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.Sampling point
Analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Embodiment 5
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：100 parts of styrene-butadiene latex SBR1712,5.0 parts of detergent alkylates are initially charged in polymeric kettle
Sodium sulfonate, 10 parts of CS2, stirring, heating, when kettle temperature degree to be polymerized reaches 50 DEG C, are rapidly added under agitation 0.24 part of nothing
Water alchlor, when system becomes orange red add 15 parts of MAH, stirring reaction 4.0hr, add 15 parts of mass concentrations be
5.0% diluted hydrochloric acid aqueous solution terminating reaction, suction filtration, washing are obtained acylated styrene-butadiene latex SBR1712 (degree of acetylation are
9.4%).
B organises the preparation of rare earth oxide：Take 100 parts of rare earth oxide (Eu2O3、CeO2And Yb2O3Mixture) and 10 parts
HDI, 500 parts of deionized waters are added in polymeric kettle, stirring mixing 30min；It is subsequently added 10 parts of polyacrylamides, stirring mixing
30min, is 12 with buffer regulation system pH value；It is subsequently adding 10 parts of neopelexes and 30 parts of acylated styrene-butadiene latexes
SBR1712 (degree of acetylation is 9.4%), stirring is warming up to 90 DEG C, after stirring reaction 5.0hr, scrubbed, dehydration, dry, grinding
The rare earth oxide that organises is obtained.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：Take 100 parts of styrene-butadiene latex SBR1712 (dry glue) and 10
Part neopelex, 600 parts of deionized waters are added to stirring mixing 30min in condensing field, be subsequently adding 400 parts it is organic
Change rare earth oxide, be 12 with buffer regulation system pH value, when being warming up to 90 DEG C, stirring mixing 3.0hr is subsequently adding 6 parts
Nitric acid is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.Take
Sample is analyzed：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Comparative example 1
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：With embodiment 1.
B organises the preparation of rare earth oxide：With embodiment 1.
(2) preparation of environment-friendly type alkene soil oxide/butadiene-styrene rubber composition：Other conditions are same as Example 1, and difference exists
Organise in preparation process rare earth oxide addition be 100 parts, i.e.,：Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and
5 parts of neopelexes, 300 parts of deionized waters are added to stirring mixing 10min in condensing field, and being subsequently adding 100 parts has
Machine rare earth oxide, is 10 with buffer regulation system pH value, and when being warming up to 60 DEG C, stirring mixing 1.0hr is subsequently adding 3
Part hydrochloric acid is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.
Sample analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Comparative example 2
The preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：Other conditions are same as Example 2, and difference is
The rare earth oxide that organises is not added with preparation process, but adds unmodified rare earth oxide, its addition is 260 parts, i.e.,：
Take 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 6 parts of neopelexes, 400 parts of deionized waters are added in condensing field
Stirring mixing 15min, is subsequently adding 260 parts of unmodified rare earth oxides, is 11 with buffer regulation system pH value, is warming up to
When 70 DEG C, stirring mixing 1.5hr is subsequently adding 4 parts of hydrochloric acid and is condensed, and last scrubbed, dehydration, dry, briquetting are obtained ring
Guarantor's type rare earth oxide/butadiene-styrene rubber composition.Sample analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Comparative example 3
(1) organise the preparation of rare earth oxide：
B organises the preparation of rare earth oxide：Other conditions are same as Example 3, and difference is to be not added with preparation process
Enter acylated styrene-butadiene latex SBR1500 (degree of acetylation is 8.1%), but add styrene-butadiene latex SBR1500, its addition is 25
Part, i.e.,：Take 100 parts of rare earth oxide (La2O3、CeO2And Pr2O3Mixture) and 8.5 parts of HTDI, 400 parts of deionized waters be added to
In polymeric kettle, stirring mixing 20min；It is subsequently added 8 parts of polyacrylamides, stirring mixing 20min, with buffer regulation system pH
It is worth for 11；7 parts of neopelexes and 25 parts of styrene-butadiene latex SBR1500 are subsequently adding, stirring is warming up to 80 DEG C, and stirring is anti-
After answering 4.0hr, scrubbed, dehydration, dry, grinding are obtained the alkene soil oxide a that organises.
(2) preparation of rare earth oxide/butadiene-styrene rubber composition：Other conditions are same as Example 3, and difference is to prepare
During be not added with the rare earth oxide that organises, but add the rare earth oxide a that organises, its addition is 300 parts, i.e.,：Take 100
Part styrene-butadiene latex SBR1500 (dry glue) and 8 parts of neopelexes, 500 parts of deionized waters are added in condensing field and stir
Mixing 20min, is subsequently adding 300 parts of rare earth oxide a that organise, and is 11 with buffer regulation system pH value, is warming up to 80 DEG C
When, stirring mixing 2.0hr is subsequently adding 5 parts of hydrochloric acid and is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type
Rare earth oxide/butadiene-styrene rubber composition.Sample analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Comparative example 4
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：With embodiment 3.
B organises the preparation of rare earth oxide：Other conditions are same as Example 3, and difference is to be not added with preparation process
Enter HTDI, i.e.,：Take 100 parts of rare earth oxide (La2O3、CeO2And Pr2O3Mixture) and 400 parts of deionized waters be added to polymeric kettle
In, stirring mixing 20min；8 parts of polyacrylamides are subsequently added, stirring mixing 20min is with buffer regulation system pH value
11；7 parts of neopelexes and 25 parts of acylated styrene-butadiene latex SBR1500 (degree of acetylation is 8.1%) are subsequently adding, are stirred
80 DEG C, after stirring reaction 4.0hr are warming up to, scrubbed, dehydration, dry, grinding are obtained the rare earth oxide b that organises.
(2) preparation of rare earth oxide/butadiene-styrene rubber composition：Other conditions are same as Example 4, and difference is to prepare
During be not added with the rare earth oxide that organises, but add the rare earth oxide b that organises, its addition is 320 parts, i.e.,：Take 100
Part styrene-butadiene latex SBR1500 (dry glue) and 9 parts of neopelexes, 550 parts of deionized waters are added in condensing field and stir
Mixing 25min, is subsequently adding 320 parts of rare earth oxide b that organise, and is 11 with buffer regulation system pH value, is warming up to 85 DEG C
When, stirring mixing 2.5hr is subsequently adding 5.5 parts of hydrochloric acid and is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environmental protection
Type rare earth oxide/butadiene-styrene rubber composition.Sample analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
Comparative example 5
(1) organise the preparation of rare earth oxide：
A is acylated the preparation of styrene-butadiene latex：With embodiment 5.
B organises the preparation of rare earth oxide：Other conditions are same as Example 5, and difference is acylated in preparation process
The addition of styrene-butadiene latex SBR1712 (degree of acetylation is 9.4%) is 7 parts, i.e.,：Take 100 parts of rare earth oxide (Eu2O3、CeO2
And Yb2O3Mixture) and 10 parts of HDI, 500 parts of deionized waters be added in polymeric kettle, stirring mixing 30min；It is subsequently added 10 parts
Polyacrylamide, stirring mixing 30min, is 12 with buffer regulation system pH value；It is subsequently adding 10 parts of DBSAs
Sodium and 7 parts of acylated styrene-butadiene latex SBR1712 (degree of acetylation is 9.4%), stirring is warming up to 90 DEG C, after stirring reaction 5.0hr, Jing
Washing, dehydration, dry, grinding are obtained the rare earth oxide c that organises.
(2) preparation of rare earth oxide/butadiene-styrene rubber composition：Other conditions are same as Example 5, and difference is to prepare
During be not added with the rare earth oxide that organises, but add the rare earth oxide c that organises, its addition is 400 parts, i.e.,：Take 100
Part styrene-butadiene latex SBR1712 (dry glue) and 10 parts of neopelexes, 600 parts of deionized waters are added in condensing field and stir
Mixing 30min, is subsequently adding 400 parts of rare earth oxide c that organise, and is 12 with buffer regulation system pH value, is warming up to 90 DEG C
When, stirring mixing 3.0hr is subsequently adding 6 parts of nitric acid and is condensed, and last scrubbed, dehydration, dry, briquetting are obtained environment-friendly type
Rare earth oxide/butadiene-styrene rubber composition.Sample analysis：Standard specimen is made in Jing sulfurations, and test performance is shown in Table 1.
The performance of 1 rare earth oxide of table/butadiene-styrene rubber composition
Claims (20)
1. a kind of butadiene-styrene rubber composition for X-ray protection, in parts by mass, including following components：
(1) styrene butadiene rubber latex (dry glue) 100%
(2) organise rare earth oxide 200~400%
Characterized in that, the described rare earth oxide that organises initially with surfactant aliphatic diisocyanate to rare earth
Oxide surface carries out Esterification process, is then isolated using amide-type water soluble polymer, is then being urged using acid anhydrides
Acylation reaction is carried out to styrene-butadiene latex in the presence of agent, subsequently its particle surface cladding is processed to be prepared from.
2. composition as claimed in claim 1, it is characterised in that the rare earth oxide is selected from single rare earth oxide, or
Person is the mixture of any two in single rare earth oxide or two kinds of any of the above proportionings, the chemistry of single rare earth oxide
Formula formula is：RxOy, wherein R are La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.
3. the composition as described in any one of claim 1 or 2, it is characterised in that the purity of the rare earth oxide is more than
99.5%, grain diameter is 0.1~5 μm.
4. composition as claimed in claim 1, it is characterised in that the surfactant is aliphatic diisocyanate, choosing
From hexamethylene diisocyanate, IPDI, the diisocyanate of dicyclohexyl methyl hydride one 4,4 ', methyl ring
One kind in hexane diisocyanate.
5. composition as claimed in claim 4, it is characterised in that the surfactant is the isocyanic acid of hexahydrotoluene two
Ester.
6. composition as claimed in claim 1, it is characterised in that it is main chain that the amide-type water soluble polymer is polyolefin
The polymer of structure, selected from polyacrylamide, polyacrylic acid, polymethylacrylic acid, poly hydroxy ethyl acrylate, polyhexene acyl
One kind in amine.
7. composition as claimed in claim 6, it is characterised in that the amide-type water soluble polymer is polyacrylamide.
8. the composition as described in any one of claim 6 or 7, it is characterised in that the use of the amide-type water soluble polymer
Measure as 3%~10%.
9. composition as claimed in claim 1, it is characterised in that described acid anhydrides is dibasic acid anhydride compound, selected from Malaysia
One kind in acid anhydrides, succinic anhydride, maleic anhydride, phthalic anhydride.
10. composition as claimed in claim 9, it is characterised in that described acid anhydrides is phthalic anhydride.
11. compositions as claimed in claim 1, it is characterised in that the catalyst is selected from aluminum trichloride (anhydrous), borontrifluoride
One kind in boron, butter of tin, zinc dichloride.
12. compositions as claimed in claim 11, it is characterised in that the catalyst is aluminum trichloride (anhydrous), addition is
0.05~0.3 part.
13. compositions as claimed in claim 12, it is characterised in that the addition of the aluminum trichloride (anhydrous) be 0.08~
0.25 part.
14. compositions as claimed in claim 1, it is characterised in that the styrene butadiene rubber latex is by conjugated diene chemical combination
Thing and aryl ethylene class compound are formed by emulsion polymerization copolymerization.
15. compositions as claimed in claim 1, it is characterised in that the conjugated diene hydrocarbon compound is C4Class conjugated diene
Compound.
16. compositions as claimed in claim 1, it is characterised in that the aryl ethylene class compound is styrene, Alpha-Methyl
One kind in styrene, 2- propenyl benzenes, ethyl styrene and their derivative.
17. compositions as described in any one of claim 1 or 14, it is characterised in that the styrene butadiene rubber latex contains admittedly
Amount 20~45%, combinated styrene content content 15~25%, 50~200nm of latex particle size.
A kind of 18. preparation methods of the butadiene-styrene rubber composition of X-ray protection as claimed in claim 1, comprise the steps：
(1) organise the preparation of rare earth oxide：
A. it is acylated the preparation of styrene-butadiene latex：In terms of the mass parts of styrene-butadiene latex (dry glue), 100 parts of butylbenzene are initially charged in polymeric kettle
Latex, 1~5 part of emulsifying agent, 5~10 parts of solvents, stirring, heating, when kettle temperature degree to be polymerized reaches 25~50 DEG C, in stirring condition
Under be rapidly added 0.05~0.3 part of catalyst, when system becomes orange red add 9~15 parts of acid anhydrides, stirring reaction 1~
4h, 10~15 parts of mass concentrations of addition are 1.5%~5.0% diluted hydrochloric acid aqueous solution terminating reaction, and suction filtration, washing are obtained and are acylated
Styrene-butadiene latex.
B. organise the preparation of rare earth oxide：Based on the mass parts of rare earth oxide, take 100 parts of rare earth oxides and 5.0~
10.0 parts of surfactants, 300~500 parts of deionized waters are added in polymeric kettle, stirring 10~30min of mixing；It is subsequently added 3
~10 parts of amide-type water soluble polymers, stirring 10~30min of mixing, is 9~12 with buffer regulation system pH value；Then plus
Enter 5~10 parts of emulsifying agents and 10~30 parts of acylated styrene-butadiene latexes, stirring is warming up to 50~90 DEG C, after 3~5hr of stirring reaction, Jing
Washing, dehydration, dry, grinding are obtained the rare earth oxide that organises.
(2) preparation of environment-friendly type rare earth oxide/butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex (dry glue), 100 are taken
Part styrene-butadiene latex (dry glue) and 5~10 parts of emulsifying agents, 300~600 parts of deionized waters be added to stirring in condensing field mix 10~
30min, is subsequently adding 200~400 parts of rare earth oxides that organise, and is 9~12 with buffer regulation system pH value, is warming up to 60
When~90 DEG C, stirring 1~3hr of mixing is subsequently adding 3~6 parts of flocculating agents and is condensed, last scrubbed, dehydration, dry, pressure
Block is obtained environment-friendly type rare earth oxide/butadiene-styrene rubber composition.
19. methods as claimed in claim 18, it is characterised in that the buffer is selected from sodium carbonate, sodium acid carbonate, hydroxide
One kind in sodium, ammoniacal liquor, ammonium hydrogen carbonate.
20. methods as claimed in claim 19, it is characterised in that the buffer is NaOH.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109897248A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | A kind of preparation method of the rubber composition of filling carbon nano-pipe |
| CN109897244A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | The preparation method of the rubber composition of the carbon nanotube of type containing high dispersive |
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2016
- 2016-10-28 CN CN201610948545.4A patent/CN106674663A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897248A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | A kind of preparation method of the rubber composition of filling carbon nano-pipe |
| CN109897244A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | The preparation method of the rubber composition of the carbon nanotube of type containing high dispersive |
| CN109897248B (en) * | 2017-12-07 | 2021-05-28 | 中国石油天然气股份有限公司 | Preparation method of rubber composition filled with carbon nanotubes |
| CN109897244B (en) * | 2017-12-07 | 2021-07-02 | 中国石油天然气股份有限公司 | Preparation method of rubber composition containing high-dispersion carbon nano-tube |
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