CN104151497A - Rubber blended macromolecular compatibilizer, preparation method and purpose - Google Patents
Rubber blended macromolecular compatibilizer, preparation method and purpose Download PDFInfo
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Abstract
The invention discloses a rubber blended macromolecular compatibilizer, a preparation method and a purpose, wherein the rubber blended macromolecular compatibilizer adopts cis-1,4-polyisoprene as the main chain, acrylate copolymer is subjected to 60C-gamma-ray radiation grafting to acquire macromolecular compatibilizer, the raw material is water-based natural latex NRL, and acrylate monomer is emulsified in water before being used, so that air pollution caused by the use of a large quantity of organic solvent is avoided and environmental friendliness is achieved; and radiation initiated polymerization reaction is adopted, so that no heating is required, and energy conservation and emission reduction are achieved. The macromolecular compatibilizer has the compatibilization effect on the blending of NR(natural rubber) rubber and ACM(acrylate monomer) rubber; the macromolecular compatibilizer is added into the blending of the NR rubber and the ACM rubber so as to obtain a vulcanized rubber product with excellent physical and mechanical properties and hot air aging resistance; and the hot air aging resistance of NR is improved.
Description
One, technical field
The present invention relates to a kind of macromole expanding material and its production and use, specifically a kind of rubber blending macromole expanding material and its production and use, macromole expanding material of the present invention can be used as NR and the expanding material of ACM blend used time uses to improve the consistency between natural rubber and acrylic elastomer.
Two, background technology
Natural rubber (NR) is biosynthetic products, and wherein more than 90% composition is cis-Isosorbide-5-Nitrae-polyisoprene.Due to the feature of the aspects such as its chemical constitution, molecular structure and molecular weight and distribution thereof, make it under deformation, easily produce induced crystallization, and there is very high physical strength.In addition NR also has good snappiness, dynamic properties and processing characteristics, and its physical synthesis performance is better than synthetic rubber, and application surface is more extensive.But because NR insatiable hunger degree is high, chemical property is more active, make NR vulcanized article under heat or action of ultraviolet light easily with environment in oxygen, ozone, oxygenant or other active media according to the mechanism generation cracking of free radical reaction, degraded, be cross-linked, the chemical reaction such as addition, and make performance, the quality badness of its goods, be so-called aging, therefore NR cross-linked rubber goods heat aging property is poor.In order to improve the heat aging property of NR, people have carried out a large amount of NR chemical modifications and the research work of physically modified.For example: the isomerization of natural rubber, by making NR molecular chain generation isomerization rearrangement reaction generate anti-form-1,4-polyisoprene, when controlling anti-form-1, when the content of 4-polyisoprene reaches 6% left and right, its comprehensive mechanical property can not reduce, and has obviously improved again the low temperature crystallization performance of NR; The epoxidation of natural gum, even natural rubber latex and epoxy acetic acidreaction, on the molecular chain of NR, generate epoxy polar group, as long as control certain epoxidation level, can reach and can keep the original mechanical property of NR and processing characteristics, can improve significantly again the enhancement of oil resistance, resistance to air loss and white carbon black; Grafted natural rubber, NR latex and methyl methacrylate carry out graft copolymerization and obtain methyl methacrylate rubber, it is higher that this chemically modified robber has tensile strength, and shock resistance, the resistance to cracking that circumnutates, dynamic fatigue and tackiness be feature, at present commercialization preferably all.The method of chemical modification can be by the screening of polymer design, raw material and synthetic method and technique, change the chain structure of superpolymer from molecular level, and optimize method and the technique of its forming process, obtain the suitable goods of condensed state structure, thereby reach improvement, improve the object of its performance, but this method production link is many, and cost is high.And the method for physically modified is comparatively easy, therefore superpolymer physical blending use, has become the important method of polymer modification.
Acrylic elastomer (ACM) is taking acrylic ester monomer compound as main, the elastomerics forming with the monomer copolymerization on a small quantity with activity of cross-linking reaction group.Its cross-linked rubber has good heat-resisting, weather-proof, resistance to ozone ageing, heat-resistant oil performance, especially, in the deep fat of chloride, sulphur, phosphorus compound polar additives, has the unrivaled performance of other rubber.Therefore it be a kind of between paracril and viton special synthetic rubber, can be used for manufacturing the sealing article of heat-resisting (175 DEG C of life-time service), oil resistant in aviation, navigation, machinery and automotive industry.According to the difference of cross-linking monomer in ACM, acrylic elastomer can be divided into epoxy type, reactive chlorine type, carboxylic acid type and non-conjugated diene type etc.Selling in the market more is reactive chlorine type rubber, and its vulcanization system mainly contains soap/sulfur cross-linking system, polyamine compounds vulcanization system and trithiocyanuric acid vulcanization system.According to polymer blended modification theory, if by suitable method and Technology, by appropriate ACM and NR blend use, ACM heat-resistant quality is combined with NR excellent comprehensive performance, will inevitably make the range of application of NR obtain larger expansion.
But because NR and ACM solubility parameter (NR approximately 16.8, ACM approximately 21) differ larger, belong to the incompatible system of thermodynamics.If the two is carried out to simple physical mechanical blend, blend can present larger Phase Separating Morphology, and the vulcanization system of the two is also different simultaneously, so and poor with vulcanized mechanical.If designed by polymer, developing suitable expanding material increases the consistency of the two, can be under mechanical shear stress effect, impel ACM dispersed in NR, and by optimizing blend covulcanization system and sulfuration process with glue, and form taking ACM as disperse phase, NR is the heterogeneous condensed state structure of microphase-separated of external phase, make to produce between the two synergistic effect, give full play to the strong point of performance separately, make blend heat-resisting, that oil resistance is better than pure NR and use elastomeric material and vulcanized article thereof.There is no report about the compatibilizing and co-mixing of NR and ACM and with studying at present.
Three, summary of the invention
The present invention aims to provide a kind of rubber blending macromole expanding material and its production and use, and macromole expanding material of the present invention is to use to improve the consistency between natural rubber and acrylic elastomer as NR and the expanding material of ACM blend used time.
Macromole expanding material of the present invention is taking cis-Isosorbide-5-Nitrae-polyisoprene as main chain, passes through
60the macromole expanding material that Co-gamma-radiation radiation grafting acrylic acid esters co-polymer obtains.Because the content of cis-Isosorbide-5-Nitrae-polyisoprene in NR is up to more than 90%, therefore the main chain of macromole expanding material and NR are completely compatible, and its side chain is the multipolymer of acrylate, and close with the molecular composition of ACM, therefore side chain and ACM have good consistency.So macromole expanding material of the present invention is from molecular structure and analyze in theory, there is " amphiphilic " property, i.e. main chain " affine NR " and side chain " affine ACM ", therefore can be used as NR and the use of the expanding material of ACM blend used time.
The preparation process of rubber blending macromole expanding material of the present invention is as follows:
(1) natural rubber latex (NRL latex), thinner, auxiliary agent A and auxiliary agent C are added in reactor, be uniformly mixed and obtain compound a;
Described thinner is pure water, and addition is the 80-120% of described natural rubber latex quality;
Described auxiliary agent A is one or more in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, bromination dodecyl trimethyl ammonium, tween, and the addition of described auxiliary agent A is the 3-5% of described natural rubber latex quality;
One or more in the hydrochloric acid soln that described auxiliary agent C is mass concentration 1.0%, the phosphoric acid solution of mass concentration 0.5%, tetracol phenixin, ethanol, iron protochloride, cuprous chloride, ferric ammonium sulfate, the addition of described auxiliary agent C is the 0.5-2% of described natural rubber latex quality.
(2) under protection of inert gas, in compound a, drip acrylic ester monomer B, after dripping off under room temperature 150-200rpm stirring reaction 1 hour, acrylic ester monomer B is uniformly dispersed and under the effect of auxiliary agent A with emulsifying water, obtain compound b; Described rare gas element is nitrogen, carbonic acid gas or argon gas;
Described acrylic ester monomer B is one or more in butyl acrylate, butyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, methyl methacrylate, glycidyl methacrylate, hydroxyethyl methylacrylate, and the addition of described acrylic ester monomer B is the 10-30% of described natural rubber latex quality.
(3) described compound b is moved in radiation chamber, with
60co-gamma-radiation irradiation (activity is 10,000-100,000 Curie), radiation dose rate is 1-5KGy/h, irradiation time is 1-5h;
(4) by the emulsion obtaining after step (3) irradiation successively through breakdown of emulsion, centrifugation, washing, obtain macromole expanding material head product after dry;
Described breakdown of emulsion is to add emulsion splitter in the emulsion obtaining after irradiation, stirs and standing 30min after adding; Described emulsion splitter is the ethanolic soln of the formic acid of mass concentration 40%, and the addition of emulsion splitter is counted the 3.5-4.0% of the quality of the emulsion obtaining after irradiation with formic acid; Emulsion after breakdown of emulsion is collected to condensation product by centrifugation, then successively through 35-40vt% (concentration expressed in percentage by volume, ethanolic soln, 10-15vt% ethanolic soln, pure water washing down together), in microwave dryer (microwave frequency 2450MHz), 115 DEG C of dry 13-15min obtain macromole expanding material head product subsequently.
(5) by described macromole expanding material head product by solvent extraction purifying after, at 50 DEG C, vacuum-drying 24h obtains macromole expanding material sterling; Extraction solvent is acetone, butanone or mibk.
Solvent extraction purification process process is: macromole expanding material head product is shredded and is placed in apparatus,Soxhlet's, extract 48h at 70 DEG C, to remove Voncoat R 3310 a small amount of in product by extraction solvent Soxhlet.
The NRL latex that the present invention uses is high ammonia natural rubber revertex, and total solid content is 62%, and total gum content is 60%.Cis-Isosorbide-5-Nitrae-polyisoprene macromole in NRL latex and the radiation graft polymerization chemical reaction of acrylic ester monomer B are the cores of preparing macromole expanding material.Drip acrylic ester monomer B and make it obtain good emulsification, being evenly dispersed in NRL,
60under Co-gamma-radiation irradiation, on cis-Isosorbide-5-Nitrae-polyisoprene molecular chain, produce macromolecular radical, acrylic ester monomer B is caused graft copolymerization occurs by free radical.Inert protective gas can prevent free radical and airborne combination with oxygen and consume, to ensure that trigger monomer carries out graft polymerization reaction.Meanwhile, under irradiation, the molecule of part acrylic ester monomer B is activated into free radical, and auto-polymerization occurs, and uses solvent extraction purifying can remove the homopolymer that is wrapped in the acrylic ester monomer in product, and obtains comparatively pure macromole expanding material.Add kind and the mass fraction of acrylic ester monomer component in emulsion to and change the condition of radiation graft polymerization by change, can obtain different model macromole expanding material.
Compared with prior art, the present invention has the following advantages:
1, the synthetic macromole expanding material of the present invention, to the blend of NR rubber and ACM rubber and with having compatibilization.Add and use macromole expanding material of the present invention in above-mentioned two kinds of glue blend and in using, can make the good vulcanized rubber article of physical and mechanical properties and heat-resistant air aging property, focused on improving the heat-resistant air aging property of NR.
2, macromole expanding material of the present invention adopts
60co-gamma-radiation irradiation emulsion grafting polymerization method is carried out acrylic ester monomer copolymerized grafting, and raw material is waterborne nature latex NRL, uses, thereby avoid using a large amount of organic solvents and the atmospheric pollution that brings environmental protection after acrylic ester monomer emulsifying water; The mode of radiation-induced polymerization, without heating, energy-saving and emission-reduction.
Four, brief description of the drawings
Fig. 1 is the Fourier transform infrared spectroscopy figure of the macromole expanding material prepared of the present invention.
Fig. 2 adds NR/ACM macromole expanding material and that do not add macromole expanding material the DSC curve with rubber unvulcanizate.
Fig. 3, Fig. 4 are NR/ACM=80/20 the rubber unvulcanizate TEM photo with increase-volume, and wherein the magnification of Fig. 3 is 0.5 ten thousand times, and the magnification of Fig. 4 is 10,000 times.
Five, embodiment
Following examples are concrete grammars of synthetic macromolecule expanding material.The high ammonia natural rubber revertex using in synthetic is three tree board natural rubber latexes of import Thailand (solid content is 62%, and drc is 60%).In following embodiment, NRL latex is quantitatively 100 parts (mass fractions), and other raw material is to account for the mass percent of NRL.
Embodiment 1:
In the present embodiment, the raw material of macromole expanding material is configured to: 100 parts, NRL latex, thinner pure water 100%, auxiliary agent A sodium lauryl sulphate 3%, acrylic ester monomer B butyl acrylate 18%, auxiliary agent celite acid solution 0.6% (mass concentration 1.0%), ethanol 0.3%, iron protochloride 0.3%.
Macromole expanding material (code name NB-X in the present embodiment
1, wherein X
1for the percentage of grafting recording, lower same) preparation according to the following steps:
(1) NRL latex, thinner, auxiliary agent A and auxiliary agent C are added in reactor, be uniformly mixed and obtain compound a;
(2) under nitrogen protection, in compound a, drip acrylic ester monomer B, after dripping off under room temperature 200rpm stirring reaction 1 hour, acrylic ester monomer B is uniformly dispersed and under the effect of auxiliary agent A with emulsifying water, obtain compound b;
(3) described compound b is moved in radiation chamber, with
60co-gamma-radiation irradiation (activity is 10,000-100,000 Curie), radiation dose rate is 3KGy/h, irradiation time is 2h;
(4) in the emulsion obtaining after irradiation, add emulsion splitter, after adding, stir and standing 30min; Described emulsion splitter is the ethanolic soln of the formic acid of mass concentration 40%, and the addition of emulsion splitter is counted 3.5% of the quality of the emulsion obtaining after irradiation with formic acid; Emulsion after breakdown of emulsion is collected to condensation product by centrifugation, then successively through 200mL 35vt% ethanolic soln, 200mL10vt% ethanolic soln, the washing of 200mL pure water, in microwave dryer (microwave frequency 2450MHz), 115 DEG C of dry 13min obtain macromole expanding material head product subsequently.
(5) macromole expanding material head product is shredded and is placed in apparatus,Soxhlet's, extract 48h at 70 DEG C by acetone Soxhlet, to remove Voncoat R 3310 a small amount of in product, at 50 DEG C, vacuum-drying 24h obtains macromole expanding material sterling subsequently.
Embodiment 2:
In the present embodiment, the raw material of macromole expanding material is configured to: 100 parts, NRL latex (quality), thinner distilled water 95%, auxiliary agent A sodium lauryl sulphate 4.5%, acrylic ester monomer B methyl methacrylate 24%, butyl acrylate 6%, auxiliary agent celite acid solution 0.5% (mass concentration 1.0%), ethanol 0.4%, iron protochloride 0.3%.
Macromole expanding material (code name NBMM-X in the present embodiment
2) preparation method with embodiment 1, in step (2) that different is, rare gas element is argon gas; In step (5), Soxhlet extraction solvent is butanone.
Embodiment 3:
In the present embodiment, the raw material of macromole expanding material is configured to: 100 parts, NRL latex (quality), thinner distilled water 95%, auxiliary agent A sodium lauryl sulphate 4.5%, acrylic ester monomer B methyl methacrylate 22%, butyl acrylate 8%, auxiliary agent C tetracol phenixin 0.6%, ethanol 0.2%, ferric ammonium sulfate 0.5%.
Macromole expanding material (code name NBMM-X in the present embodiment
3) preparation method with embodiment 2.
Embodiment 4:
In the present embodiment, the raw material of macromole expanding material is configured to: 100 parts, NRL latex (quality), thinner distilled water 100%, auxiliary agent A sodium lauryl sulphate 5%, acrylic ester monomer B methyl acrylate 15%, ethyl propenoate 10%, butyl acrylate 5%, auxiliary agent C tetracol phenixin 0.5%, ethanol 0.3%, iron protochloride 0.4%, ferric ammonium sulfate 0.2%.
Macromole expanding material (code name NMEB-X in the present embodiment
4) preparation method with embodiment 1.
Embodiment 5:
In the present embodiment, the raw material of macromole expanding material is configured to: 100 parts, NRL latex (quality), thinner distilled water 100%, auxiliary agent A sodium lauryl sulphate 5%, acrylic ester monomer B methyl acrylate 10%, ethyl propenoate 5%, methyl methacrylate 15%, auxiliary agent C phosphoric acid solution 0.8% (mass concentration 0.5%), cuprous chloride 0.3%.
Macromole expanding material (code name NMEMM-X in the present embodiment
5) preparation method with embodiment 1.
[structural characterization of macromole expanding material of the present invention and application test]
1, the mensuration of macromole expanding material percentage of grafting
Application weighting method, according to following formula, is calculated the percentage of grafting of the macromole expanding material of different monomers, different ratios.
The operation steps that percentage of grafting is measured:
1) according to the regulation of GB GB/T 8298-2008, the total solid content of high ammonia concentrated natural latex (NRL) for test experiments, test result is 62%; According to the NR drc in the regulation test NRL of GB GB/T 8299-2008, test result is 60% again;
2) get the natural rubber latex X/g before the irradiation grafting of certain mass, calculate NR dry glue quality Y/g wherein
Y=X × 60% (NR drc in NRL) (2)
3) get the emulsion after above-mentioned irradiation grafting, the treated macromole expanding material sterling that obtains, weighs.
Combined type (1), calculates X in embodiment 1-5
1-X
5be respectively: 23,29,30,26,21.
2, the Infrared Characterization of macromole expanding material
Series samples prepared by embodiment of the present invention 1-5 is carried out attenuated total reflectance (ATR) ftir analysis, and the infrared spectrogram obtaining as shown in Figure 1.
As can be seen from Fig. 1, infrared absorption wavelength 1660cm
-1place is the stretching vibration absorption peak of unsaturated carbon-carbon double bond (C=C) on c-cis-Isosorbide-5-Nitrae-polyisoprene molecular backbone chain, absorption peak 815cm
-1left and right is the stretching vibration absorption peak of unsaturated carbon hydrogen bond (=C-H) on its molecular backbone chain, absorption peak 1740cm
-1place is the stretching vibration absorption peak of carbonyl (C=O) in the monomeric unit of acrylic ester copolymerization thing side chain, 1150cm
-1left and right is the stretching vibration absorption peak of carbon oxygen singly-bound (C-O) in ester group.Serial macromole expanding material of the present invention is the graft copolymer of acrylic ester monomer and cis-Isosorbide-5-Nitrae-polyisoprene really as seen from Figure 1.
3, the application test of macromole expanding material
1) test site: Anhui Anda Zhongding Rubber Technology Development Co., Ltd.'s Hefei AnHui University Science & Technology Park
2) method for making sample: NR/ACM is also to adopt the method for master batch blend to carry out with the calendering process of glue, according to the ratio of certain NR and ACM rubber, calculate and take the synthetic macromole expanding material of NR master batch, ACM master batch and the present invention, in mill, thin-pass is played triangle bag 8-10 time, and 8-10 lower sheet of 3mm thickness clot obtains the rubber unvulcanizate of NR/ACM blend use.
The NR/ACM making as stated above, also with rubber unvulcanizate 170 DEG C × 6min of press vulcanization in vulcanizing press, is specified to cut to the test sample of cross-linked rubber according to GB 2941-2006.
The preparation method of NR master batch and ACM master batch is: in the mill that is connected with water coolant, respectively according to the formula of NR master batch and ACM master batch, add successively rubber, softening agent, anti-aging agent, reinforcement system, vulcanization system, to be mixedly roll spacing is adjusted to minimum after evenly, thin-pass is played triangle bag 5-8 time, adjust roll spacing to 5-8 rear lower sheet of 3mm left and right clot, make respectively the master batch of NR and ACM.The experimental formula of NR master batch and ACM master batch is:
NR master batch formula (mass fraction): natural rubber domestic standard 5
#glue SCR5
#100, anti-aging agent RD 1, antioxidant A 1, antioxidant 4010NA 1.5, high wear-resistant carbon black N550 50, ZnO 5, stearic acid SA 1, Sulfur S-60 3, altax 0.5; Mass fraction adds up to 163.
ACM master batch formula (mass fraction): acrylic elastomer ZEON-AR72LS 100, anti-aging agent 18D 0.5, anti-aging agent KY405 1.5, inner pattern releasing agent applicable VAM 0.5, high wear-resistant carbon black N550 50, sodium stearate NSA 8, Sulfur S-80 1; Mass fraction adds up to 161.5.
If by NR and ACM by rubber mass fraction m:(100-m) carry out and use blend, NR master batch and ACM master batch ratio of quality and the number of copies should be:
The consumption of macromole expanding material is and uses the 3-8% of rubber total mass umber.Conventionally,, as the also ACM rubber mass fraction increase of use, the consumption of expanding material is also wanted corresponding increase.But because the price of acrylic elastomer ACM is higher, simultaneously and consumption many can obviously affect the comprehensive mechanical property of natural gum NR, so the rubber of NR/ACM use generally more proper in 80/20 left and right than (mass fraction).
3) testing method: stretching and tear resistance are tested according to the regulation of GB 528-1982, draw speed 500mm/min; Shore a hardness is tested according to the regulation of GB/T 531, test thickness 6mm; Resistance to air oven aging test is according to the regulation of GB/T 3512-2001, and selection condition is 100 DEG C × 24h.
4) test-results
Macromole expanding material product of the present invention is used at NR and ACM and in using, and formula and performance are in table 1.
Table 1 uses the cured properties comparison of this NR/ACM rubber compatilizer
* the ratio of NR rubber and the blend of ACM rubber use is NR/ACM=80/20 (mass fraction);
The addition of macromole expanding material is 5% of rubber total mass.
The basic physical and mechanical properties of cross-linked rubber is more visible, and the poor-performing simply NR and ACM blend postcure being obtained is all lower than the tensile strength of the independent component of NR and elongation, there is no the effect of improving NR performance.But add the cross-linked rubber sample after expanding material product of the present invention, the basic physical and mechanical properties of NR remains unchanged substantially, but heat-resistant air aging property is significantly improved.But the action effect of the macromole expanding material of each trade mark has certain difference, wherein better with the action effect of NBMM-29 and NMEB-26.
4, NR/ACM the differential heat scan dsc analysis with rubber unvulcanizate
NBMM-29 increase-volume NR/ACM with rubber unvulcanizate and increase-volume NR/ACM carry out with the sample of rubber unvulcanizate the test-results that differential scanning (DSC) analysis contrasts and see Fig. 2 not.
The DSC curve NR/ACM that short-and-medium vertical line is designated as of Fig. 2 is also with the glass transition place of two kinds of rubber in rubber unvulcanizate, and corresponding temperature is second-order transition temperature (Tg), the Tg that wherein junior is NR, the Tg that the higher person is ACM.Article two, curve comparison is visible, all there is change in the Tg that adds expanding material latter two rubber, in obviously having occurred, moves the Tg that shows two kinds of rubber, the Tg that is NR moves to high temperature direction, and the Tg of ACM moves to low temperature direction, this explanation consistency of NR and ACM two-phase in rubber unvulcanizate significantly increases, and has confirmed that NBMM-29 has played the effect of expanding material really.
5, transmission electron microscope tem observation is analyzed
Macromole expanding material NBMM-29 of the present invention also uses the rubber unvulcanizate ultrathin section(ing) of increase-volume to NR/ACM, through Si Yangization Osmium OsO
4dyeing after application transmission electron microscope observation, clap Photomicrograph as shown in Figure 3, Figure 4.
Fig. 3, Fig. 4 are NR/ACM=80/20 the rubber unvulcanizate sample with increase-volume, after perosmic anhydride solution-dyed, obtain at transmission electron microscope(TEM) arsis, and wherein dark part is the imaging of external phase NR, and light-colored part is the imaging in disperse phase ACM microfacies district.From Fig. 3, Fig. 4, macromole expanding material makes ACM disperse phase dispersed in NR external phase, the phase region size of disperse phase has also reached microphase-separated level, and simultaneously the interface of phase region intersection also thickens, and this also illustrates that it has played good compatibilization.
Claims (9)
1. a rubber blending macromole expanding material, is characterized in that: be taking cis-Isosorbide-5-Nitrae-polyisoprene as main chain, pass through
60the macromole expanding material that Co-gamma-radiation radiation grafting acrylic acid esters co-polymer obtains.
2. a preparation method for rubber blending macromole expanding material claimed in claim 1, is characterized in that comprising the following steps:
(1) natural rubber latex, thinner, auxiliary agent A and auxiliary agent C are added in reactor, be uniformly mixed and obtain compound a;
Described thinner is pure water;
Described auxiliary agent A is one or more in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, bromination dodecyl trimethyl ammonium, tween;
One or more in the hydrochloric acid soln that described auxiliary agent C is mass concentration 1.0%, the phosphoric acid solution of mass concentration 0.5%, tetracol phenixin, ethanol, iron protochloride, cuprous chloride, ferric ammonium sulfate;
(2) under protection of inert gas, in compound a, drip acrylic ester monomer B, after dripping off under room temperature 150-200rpm stirring reaction 1 hour, obtain compound b;
Described rare gas element is nitrogen, carbonic acid gas or argon gas;
The addition of described acrylic ester monomer B is the 10-30% of described natural rubber latex quality;
(3) described compound b is moved in radiation chamber, with
60co-gamma-radiation irradiation, radiation dose rate is 1-5KGy/h, irradiation time is 1-5h;
(4) by the emulsion obtaining after step (3) irradiation successively through breakdown of emulsion, centrifugation, washing, obtain macromole expanding material head product after dry;
(5) by described macromole expanding material head product by solvent extraction purifying after, at 50 DEG C, vacuum-drying 24h obtains macromole expanding material sterling.
3. preparation method according to claim 2, is characterized in that:
Described in step (1), the addition of thinner is the 80-120% of described natural rubber latex quality, and the addition of described auxiliary agent A is the 3-5% of described natural rubber latex quality; The addition of described auxiliary agent C is the 0.5-2% of described natural rubber latex quality.
4. preparation method according to claim 2, is characterized in that:
Described in step (2), rare gas element is nitrogen, carbonic acid gas or argon gas.
5. preparation method according to claim 2, is characterized in that:
Described in step (2), acrylic ester monomer B is one or more in butyl acrylate, butyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, methyl methacrylate, glycidyl methacrylate, hydroxyethyl methylacrylate.
6. preparation method according to claim 2, is characterized in that:
In step (3)
60the activity of Co-gamma-radiation irradiation is 10,000-100,000 Curie.
7. preparation method according to claim 2, is characterized in that:
Step (4) is to add emulsion splitter in the emulsion obtaining after step (3) irradiation, stirs and standing 30min after adding; Described emulsion splitter is the ethanolic soln of the formic acid of mass concentration 40%, and the addition of emulsion splitter is counted the 3.5-4.0% of the quality of the emulsion obtaining after irradiation with formic acid; Emulsion after breakdown of emulsion is collected to condensation product by centrifugation, and then, successively through 35-40vt% ethanolic soln, 10-15vt% ethanolic soln, pure water washing, in microwave dryer, 115 DEG C of dry 13-15min obtain macromole expanding material head product subsequently.
8. preparation method according to claim 2, is characterized in that:
In step (5), extraction solvent is acetone, butanone or mibk.
9. a purposes for rubber blending macromole expanding material claimed in claim 1, is characterized in that: use to improve the consistency between natural rubber and acrylic elastomer as expanding material in natural rubber and acrylic elastomer blend used time.
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| CN105445155A (en) * | 2015-12-24 | 2016-03-30 | 上海微谱化工技术服务有限公司 | Analysis method of particle size of carbon black in cis-1,4-polybutadiene rubber |
| CN110894297A (en) * | 2019-12-06 | 2020-03-20 | 安徽大学 | Preparation of rubber-used macromolecular compatibilizer and application of macromolecular compatibilizer in acrylate rubber/nitrile rubber alloy elastomer |
| CN110894297B (en) * | 2019-12-06 | 2022-02-25 | 安徽大学 | Preparation of rubber-used macromolecular compatibilizer and application of macromolecular compatibilizer in acrylate rubber/nitrile rubber alloy elastomer |
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