CN1152082C - Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof - Google Patents
Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof Download PDFInfo
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- CN1152082C CN1152082C CNB008164509A CN00816450A CN1152082C CN 1152082 C CN1152082 C CN 1152082C CN B008164509 A CNB008164509 A CN B008164509A CN 00816450 A CN00816450 A CN 00816450A CN 1152082 C CN1152082 C CN 1152082C
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- rubber
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- acrylate
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- 239000005060 rubber Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims description 33
- 239000002245 particle Substances 0.000 title claims description 29
- 229920000126 latex Polymers 0.000 claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 229920003023 plastic Polymers 0.000 claims abstract description 19
- 239000004033 plastic Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims description 61
- 239000004816 latex Substances 0.000 claims description 37
- 238000004132 cross linking Methods 0.000 claims description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
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- 239000000203 mixture Substances 0.000 claims description 16
- -1 (methyl) Octyl Chemical group 0.000 claims description 14
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- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004258 Ethoxyquin Substances 0.000 claims description 2
- 229920002449 FKM Polymers 0.000 claims description 2
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- 239000007983 Tris buffer Substances 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
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- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
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- 229910052802 copper Inorganic materials 0.000 description 10
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 5
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- 229910052710 silicon Inorganic materials 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CKDAPHXLBCKEKI-UHFFFAOYSA-N C=CC=C.C(=O)(O)C(C#N)=C Chemical compound C=CC=C.C(=O)(O)C(C#N)=C CKDAPHXLBCKEKI-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a full-vulcanized powdered rubber with a controllable grain diameter of 20 to 200 nm, a preparation method thereof and a purpose thereof. Rubber latex of which the graindiameter is 20 to 2000 nms is irradiated by a high-energy radiation source to prepare the powdered rubber. The powdered rubber is easily dispersed in a plastic parent matrix, and thus, the powdered rubber can be combined with various plastics to manufacture various toughening plastics and thermoplastic elastic bodies.
Description
The present invention relates to powdered rubber, more particularly, the present invention relates to the to have controllable grain size fully vulcanized powder rubber of (can reach nano level) and the Preparation method and use of this powdered rubber.
As everyone knows, rubber is generally bulk, bar-shaped, powdery, granular or sheet etc., and powdered rubber has the branch of not sulfuration (comprising slight sulfuration) and sulfuration again.In sulfide powder rubber, except that the sulfurized silicon rubber powder by the chemical crosslink technique preparation, other sulfide powder rubber is not seen bibliographical information.
Document to sulfurized silicon rubber powder and preparation method thereof report is more, and for example U.S. Patent No. 4743670 discloses a kind of preparation method of sulfurized silicon rubber powder He this sulfurized silicon rubber powder of high dispersing in (on May 10th, 1988).This sulfurized silicon rubber powder has single-size shape and particle diameter, and volume specific resistance is greater than 10
13Ohmcm.The preparation method of this sulfurized silicon rubber powder comprises (1) in the presence of tensio-active agent, in the water of 0 ℃-25 ℃ of maintenances, and the dispersion liquid of the vulcanizable liquid silicon rubber composition of preparation heating; (2) dispersion liquid of preparation in (1) is dispersed in the liquid that remains on 50 ℃ at least, makes liquid silicon rubber composition be sulfided into powder and separate the sulfurized silicon rubber powder with (3).
U.S. Patent No. 4742142 has been reported a kind of preparation method of silicon rubber powder in (on April 6th, 1987), method according to this patent report, heat vulcanizable compositions with liquid in 0 ℃-25 ℃, it is emulsified into emulsion in containing the water of tensio-active agent, then this emulsion is sprayed in the water-bath that is at least 25 ℃ of temperature each component in the tight cure rubber composition.
U.S. Patent No. 4749765 has disclosed a kind of preparation method of silicon rubber powder of uniform grading in (on June 7th, 1988), this method comprises that (1) is under-60 ℃-+50 ℃ temperature, by each component is mixed, prepare a kind of liquid silicon rubber composition and remain under this temperature; (2) liquid silicon rubber composition of preparation in (1) is sprayed in 80 ℃-200 ℃ the warm air, generate saccharoid; (3) silicon rubber powder of preparation is reclaimed in the saccharoid of preparation and (4) in the sulfuration (2).
U.S. Patent No. 5837793 (on November 17th, 1998) discloses a kind of sulfurized silicon rubber powder and preparation method thereof.This silicon rubber powder has the wetting ability and the soft feel(ing) of height, median size is less than 500 microns, its preparation method be (1) but sulfuration comprises the silicon sulfide ketone composition of specific organopolysiloxane, generate sulphurated siliastic and (2) sulphurated siliastic that spraying drying generated.The vulcanization reaction that generates sulphurated siliastic can be that condensation reaction, the organo-peroxide inductive between the hydrogen of the hydroxyl of addition reaction, silicon bonding between the hydrogen of alkenyl and silicon bonding and silicon bonding reacts and the reaction of ultraviolet induction.
Though prior art has been reported with chemical crosslink technique sulfurized silicon rubber powder and preparation method thereof, and other fully vulcanized powder rubber is not still had report.
Find that behind the rubber latex irradiation, drying just can be made into fully vulcanized powder rubber after the long-term deep research of inventor's process.This powdered rubber epigranular, particle diameter is controlled, and the particle diameter of rubber particles is basic identical in the particle diameter of powdered rubber and the latex.Can be used for preparing toughened plastics and fully sulfurized plastoelasticity body, have broad application prospects and great economic implications.
Therefore, the purpose of this invention is to provide a kind of full sulfurized powdered rubber.
Another object of the present invention provides the preparation method of described fully vulcanized powder rubber.
Another object of the present invention provides the composition that can be used for preparing toughened plastics and thermoplastic elastomer, and it contains fully vulcanized powder rubber of the present invention and plastics.
A further object of the invention provides the application that described fully vulcanized powder rubber is used for toughened plastics and preparation thermoplastic elastomer.
Fully vulcanized powder rubber of the present invention be a kind of gel content be 60% weight or higher, to need not separant be free flowable rubber particle.Gel content is the parameter a kind of commonly used that is used to characterize the rubber cross degree in this area, and it can be measured according to method well known in the art.The gel content of fully vulcanized powder rubber of the present invention is 60% weight or higher, preferred 75% weight or higher, most preferably 90% weight or higher.In addition, swelling index is the another kind parameter commonly used that is used to characterize the rubber cross degree in this area, and it can be measured according to method well known in the art.The swelling index of fully vulcanized powder rubber of the present invention is not more than 15, preferably is not more than 13.In addition, fully vulcanized powder rubber of the present invention is a kind of free flowable rubber particle, but and this free-flowing property need not can reach by separant.Therefore, fully vulcanized powder rubber of the present invention can not add separant, certainly, as needs, also can add separant in the fully vulcanized powder rubber of the present invention, with its flowable of further raising and resistance to blocking.
Fully vulcanized powder rubber of the present invention has controlled particle diameter, and median size is generally 20～2000nm, is preferably 30-1500nm, more preferably 50-500nm.In the present invention, particle diameter is to adopt the scanning electron microscope technical measurement.
Each particulate in the fully vulcanized powder rubber of the present invention all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
To fully vulcanized powder rubber of the present invention to the kind of rubber without any restriction, it can be except that the rubber by any kind of the chemical crosslink technique sulfurized silicon rubber, for example full sulfurized natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, chloroprene rubber, polyhutadiene, esters of acrylic acid rubber, vinylpyridiene-styrene-butadiene rubber, polyisoprene rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), thiorubber, Acrylester Butadiene Rubber, urethanes or viton.
Fully vulcanized powder rubber of the present invention is by obtaining corresponding rubber latex sulfuration with irradiation method.For example, can with the rubber latex of commercially available or homemade 20-2000 nanometer raw material, add or do not add crosslinking coagent, with the energetic ray irradiation, make its complete cure, to prepare fully vulcanized powder rubber of the present invention.The energetic ray source can be selected from cobalt source, X-ray, ultraviolet ray or high-energy electron accelerator, preferred cobalt source.The dosage of irradiation can be 0.1-30Mrad, preferred 0.5-20Mrad.With the latex drying behind the irradiation just obtain with latex in the essentially identical fully vulcanized powder rubber of rubber particles size.Drying process can carry out also can carrying out with the precipitation desiccating method with spray-dryer, if carry out with spray-dryer, inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.
When preparation fully vulcanized powder rubber of the present invention, without any restriction, can be selected from natural rubber latex, styrene butadiene rubber latex, carboxylic styrene-butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, chloroprene rubber latex, content of polybutadiene rubber latex, esters of acrylic acid rubber latex, vinylpyridiene-styrene-butadiene rubber latex, polyisoprene rubber latex, isoprene-isobutylene rubber latex, ethylene-propylene rubber(EPR) latex, thiorubber latex, Acrylester Butadiene Rubber latex, urethanes latex or fluoroelastomer latex to used rubber latex raw material.The particle diameter of rubber particle can be according to different application and difference.Solid content to rubber latex is not particularly limited, and is generally 20-70% weight, preferred 30-60% weight, more preferably 40-50% weight.
Crosslinking coagent can be do not used when preparing fully vulcanized powder rubber of the present invention, also crosslinking coagent can be used.Used crosslinking coagent can be simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.
These crosslinking coagents can the arbitrary combination mode use, as long as they help radiation vulcanization under irradiation.
The add-on of these crosslinking coagents is generally the 0.1-10% weight of gum weight with the kind and different variation of prescription of rubber latex, is preferably 0.5-9% weight, more preferably 0.7-7% weight.
Preparing the employed energetic ray of fully vulcanized powder rubber of the present invention source is general cobalt source, X-ray, ultraviolet ray or high-energy electron accelerator, preferably uses the cobalt source.The dosage of irradiation can be 0.1-30Mrad, preferred 0.5-20Mard.Irradiation dose is relevant with prescription with the kind of latex.In the ordinary course of things, irradiation dose should make the gel content of the full vulcanized rubber that obtains behind the rubber latex radiation vulcanization reach 60% weight or higher, preferred 75% weight or higher, more preferably 90% weight or higher.
Fully vulcanized powder rubber of the present invention very easily is dispersed in the plastics parent, therefore can mix with various plastics, makes various toughened plastics and thermoplastic elastomer.Basic preparation method mixes fully vulcanized powder rubber of the present invention by a certain percentage with plastics in conventional mixing equipment He under the common process condition, if desired, add processing aid and expanding material in right amount.
When the preparation toughened plastics, the weight ratio of fully vulcanized powder rubber of the present invention and plastics is 0.5: 99.5-50: 50, be preferably 1: 99-30: 70.By toughness reinforcing plastics can be nylon, polypropylene, polyethylene, polyvinyl chloride, urethane, Resins, epoxy, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide, polysulfones and multipolymer and blend.
When the preparation thermoplastic elastomer, the weight ratio of fully vulcanized powder rubber and plastics is 30: 70-75: 25, be preferably 50: 50-70: 30.The available plastics are nylon, polypropylene, polyethylene, polyvinyl chloride, urethane, Resins, epoxy, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyimide, polysulfones and multipolymer and blend.
Further describe the present invention in conjunction with the accompanying drawings with embodiment below, but scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention is determined by the accompanying Claim book.
Accompanying drawing 1 is that the magnification of the full sulfuration carboxylic styrene-butadiene rubber powder of embodiment 4 gained is 20,000 times a stereoscan photograph;
Accompanying drawing 2 is 40,000 times atomic force microscope photo for the magnification of embodiment 14 gained samples.
In following examples, gel content is measured in accordance with the following methods: accurately take by weighing about 0.1 gram of powdered rubber that spraying drying obtains, wrap with general lens paper, wrap into again in the 200 purpose copper mesh, accurately weighing, then it is boiled in toluene, the quality substantially constant after thorough drying is as the criterion boiling time with copper mesh and wrap thereof, is generally 6 hours.Copper mesh that will fully boil and wrap complete drying thereof afterwards, accurately weighing.According to following formula calculated for gel content:
Gel content (%)=[W
0-(W
1-W
2)]/W
0* 100%
In the formula: W
0The weight of expression powdered rubber sample;
W
1The weight of copper mesh and wrap thereof before expression is boiled;
W
2Expression is boiled after the weight of the copper mesh of thorough drying and wrap thereof.
Swelling index is measured in accordance with the following methods: with the rubber latex drying and forming-film behind the radiation vulanization (then directly using the exsiccant powder as the film forming difficulty).With accurate weigh is W
0The capsule made of 200 order copper mesh steep in the toluene, place a little, pulling out then weighs rapidly is designated as W
1The film (or powder) that takes by weighing about 0.1 gram is put into the copper mesh capsule, and film and copper mesh one foaming are gone in the toluene, is positioned over shady and cool place swelling after 24 hours, copper mesh is carefully pulled out together with the swollen gel, inhale fast and remove the solvent of gel surface, weigh rapidly then, weight is designated as W
2To constant weight, weight is designated as W with the copper mesh after weighing and gel finish-drying
3Swelling index calculates according to following formula:
Swelling index=(W
2-W
1)/(W
3-W
0)
Embodiment 1
With the commercially available carboxylic styrene butadiene latex of solid content 50 weight % (Yanshan Petrochemical production, the trade mark: XSBRL-54B1) 5Kg places a container, under agitation the different monooctyl ester 75g of dropwise addition of acrylic acid after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃-160 ℃, temperature out is 40 ℃-60 ℃, collects dried carboxylic styrene-butadiene rubber powder in cyclonic separator, obtains free flowable full sulfuration carboxylic styrene-butadiene rubber powdered sample 1.The particle diameter that records powdered rubber is about 150nm, and gel content is 92.6%, and swelling index is 7.6.
Embodiment 2
Except that with the 10Mrad dosage irradiation, other all with embodiment 1 in identical, obtain free flowable full sulfuration carboxylic styrene-butadiene rubber powdered sample 2.The particle diameter that records powdered rubber is about 150nm, and gel content is 94.5%, and swelling index is 5.4.
Embodiment 3
Except that crosslinking coagent with the diethylene glycol diacrylate, other is all identical with embodiment 1, obtains free flowable full sulfuration carboxylic styrene-butadiene rubber powdered sample 3.Record the powdered rubber particle diameter and be about 150nm, gel content is 93.0%, and swelling index is 7.3.
Embodiment 4
Except that crosslinking coagent with the Viscoat 295, other is all identical with embodiment 1, obtains free flowable full sulfuration carboxylic styrene-butadiene rubber powdered sample 4.The particle diameter that records powdered rubber is about 150nm (seeing accompanying drawing 1), and gel content is 93.3%, and swelling index is 5.8.
Embodiment 5
With solid content be 45% weight commercially available styrene-butadiene latex (orchidization production, the trade mark: butylbenzene-50) 5Kg places container, the different monooctyl ester 67.5g of dropwise addition of acrylic acid under agitation after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex after the radiation is by the spray-dryer spraying drying, and the inlet temperature of moisture eliminator is 140 ℃-160 ℃, and temperature out is 40 ℃-60 ℃, obtains free flowable full sulfuration styrene-butadiene rubber(SBR) powder sample 1.The particle diameter that records powdered rubber is about 100nm, and gel content is 90.0%, and swelling index is 12.9.
Embodiment 6
Except that crosslinking coagent with the Viscoat 295, other is all identical with embodiment 5, obtains free flowable full sulfuration styrene-butadiene rubber(SBR) powder sample 2.The particle diameter that records powdered rubber is about 100nm, and gel content is 90.4%, and swelling index is 11.6.
Embodiment 7
With solid content is that commercially available carboxylic acrylonitrile butadiene rubber latex (orchidization production, the trade mark the are XNBRL) 5Kg of 45 weight % places container, and under agitation the different monooctyl ester 67.5g of dropwise addition of acrylic acid after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, and the moisture eliminator inlet temperature is 140 ℃-160 ℃, and temperature out is 40 ℃-60 ℃, obtains free flowable full sulfuration carboxyl butyronitrile powdered rubber sample 1.The particle diameter that records powdered rubber is about 50nm, and gel content is 96.1%, and swelling index is 7.5.
Embodiment 8
Except that crosslinking coagent with the Viscoat 295, other is all identical with embodiment 7, obtains free flowable full sulfuration carboxyl acrylonitrile-butadiene rubber powder end sample 2.The particle diameter that records powdered rubber is about 50nm, and gel content is 97.1%, and swelling index is 6.7.
Embodiment 9
With solid content is that the commercially available butyl acrylate) latex of 48 weight % (Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing produces, and the trade mark is BC-01) 5Kg places container, and under agitation the different monooctyl ester 72g of dropwise addition of acrylic acid after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, and the inlet temperature of moisture eliminator is 140 ℃-160 ℃, and temperature out is 40 ℃-50 ℃, obtains free flowable full propylene sulfide acid butyl ester rubber powder sample 1.The particle diameter that records powdered rubber is about 100nm, and gel content is 85.7%, and swelling index is 12.2.
Embodiment 10
Except that crosslinking coagent with the Viscoat 295, other is all identical with embodiment 9, obtains free flowable full propylene sulfide acid butyl ester rubber powder sample 2.The particle diameter that records powdered rubber is about 100nm, and gel content is 87.7%, and swelling index is 11.0.
Embodiment 11
With solid content is that natural rubber latex (Beijing Emulsion Factory provides) 5Kg of 60 weight % places container, under agitation drips Viscoat 295 150g, after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 15Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, and the inlet temperature of moisture eliminator is 140 ℃-160 ℃, and temperature out is 40 ℃-50 ℃, obtains free flowable full sulfurized natural rubber powdered sample 1.The median size that records powdered rubber is about 500nm, and gel content is 94.1%, and swelling index is 12.8.
Embodiment 12
Adopt full sulfuration carboxylic styrene-butadiene rubber powdered sample 1 (embodiment 1) and the mixed of nylon 6 (1013B of Ube Industries Ltd.) with 75/25, with the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is set at respectively: 210 ℃, 225 ℃, 225 ℃, 225 ℃, 230 ℃ and 225 ℃ (head temperature).Pellet is made the standard batten with pressed disc method and injection moulding respectively, and the performance that obtains these full sulfuration carboxylic styrene-butadiene rubber/nylon 6 thermoplastic elastomers after tested is as shown in table 1.
Embodiment 13
Adopt full sulfurized natural rubber powdered sample (embodiment 11) and high-density polyethylene resin (second auxiliary factory, Beijing produces, and the trade mark the is J-1) mixed with 70/30, with Brabender kneader blend 2 minutes, the kneader oil bath temperature was 160 ℃.The two roller mills (temperature: 160 ℃) in flakes of gained sample, compressing tablet sample preparation then, the performance that records full sulfurized natural rubber/rubber/polythene thermoplastic elastomer is as shown in table 1.
Table 1
| Sample | Tensile strength (MPa) | Tension fracture elongation rate (%) | Tensile set (%) | 100% tensile modulus (MPa) | Shore hardness | Vicat softening temperature (℃) | |
| ASTM D412 | ASTM D412 | ASTM D412 | ASTM D412 | ASTM D2240- 95 | ASTM D1525 | ||
| Embodiment 12 | The compressing tablet sample preparation | 17.0 | 175 | 61 | 11.8 | --- | --- |
| The injection sample preparation | 16.4 | 216 | 101 | 10.5 | 40 (shore hardness D) | 164.8 | |
| Embodiment 13 | The compressing tablet sample preparation | 15.0 | 438 | 122 | --- | 86 (shore hardness A) | --- |
Embodiment 14
(Ube Industries Ltd. produces at nylon 6, trade mark 1013B) adds the calcium stearate of 20% full sulfuration carboxylic styrene-butadiene rubber powdered sample 1 (embodiment 1) and 0.6% and 0.8% superfine talcum powder in, (1500rpm) mixed 3 minutes at a high speed, use the ZSK-25 of WP company twin screw extruder blend granulation then, each section of forcing machine temperature is set at: 230 ℃, 235 ℃, 240 ℃, 245 ℃, 240 ℃, 235 ℃, be injection molded into the standard batten after the pellet oven dry, the performance that records super-toughened nylon 6 by the ASTM standard is as shown in table 2.The particle distribution figure that records with atomic force microscope is (particle diameter of disperse phase rubber particles is about 150nm) as shown in Figure 2.
Comparative example 1
Nylon used among the embodiment 14 6 directly is injection molded into the standard batten, and test result is as shown in table 2.
Embodiment 15
(Asahi Chemical Industry produces at polyoxymethylene, the trade mark 4520) the full sulfuration carboxylic styrene-butadiene rubber powdered sample 1 (embodiment 1) of adding 28% in, and add 1.2% calcium stearate, 0.6% superfine talcum powder, 0.3% polyethylene wax and 0.4% oxidation inhibitor IRGANOX1010 (available from Ciba-Geigy), (1500rpm) mixed 3 minutes at a high speed, use the ZSK-25 of WP company twin screw extruder blend granulation then, each section of forcing machine temperature is set at: 175 ℃, 180 ℃, 185 ℃, 185 ℃, 180 ℃, 175 ℃, be injection molded into the standard batten after the pellet oven dry, the performance that records reinforced polyformaldehyde by the ASTM standard is as shown in table 2.
Comparative example 2
Polyoxymethylene used among the embodiment 15 directly is injection molded into the standard batten, and test result is as shown in table 2.
Table 2
| Testing method | Comparative example 1 | Embodiment 14 | Comparative example 2 | Embodiment 15 | ||
| Tensile strength (MPa) | ASTM D638 | 72 | 51.5 | 62.2 | 47.2 | |
| Elongation at break (%) | ASTM D638 | 60 | 175 | 30 | 215 | |
| Flexural strength (MPa) | ASTM D790 | 80.5 | 56.6 | 82.5 | 56.7 | |
| Modulus in flexure (GPa) | ASTM D790 | 2.2 | 1.72 | 2.34 | 1.65 | |
| Izod notched Izod impact strength (J/m) | ASTM D256 | 4 5 | 665 | 42 | 562 | |
| HDT (℃) | 1.82MPa | ASTM D648 | 68.5 | 61.8 | --- | --- |
| 0.46MPa | --- | --- | 161.5 | 142.8 | ||
Claims (23)
1. one kind except that by the fully vulcanized powder rubber the sulfurized silicon rubber powder of chemical crosslink technique preparation, and its median size is 20-2000nm, and the particulate of described powdered rubber is a homogeneous, and its gel content is 60% weight or more.
2. by the described fully vulcanized powder rubber of claim 1, it is characterized in that the particle diameter of described powdered rubber is 30-1500nm.
3. by the described fully vulcanized powder rubber of claim 1, it is characterized in that the particle diameter of described powdered rubber is 50-500nm.
4. by the described fully vulcanized powder rubber of claim 1, it is characterized in that the gel content of described powdered rubber is 75% weight or more.
5. by the described fully vulcanized powder rubber of claim 1, it is characterized in that the gel content of described powdered rubber is 90% weight or more.
6. press each described fully vulcanized powder rubber of claim 1-5, it is characterized in that described rubber is selected from natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, chloroprene rubber, polyhutadiene, esters of acrylic acid rubber, vinylpyridiene-styrene-butadiene rubber, polyisoprene rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), thiorubber, Acrylester Butadiene Rubber, urethanes and viton.
7. the method for preparing each described fully vulcanized powder rubber of claim 1-6, it comprises with irradiation method vulcanizes corresponding rubber latex.
8. by the described method of claim 7, it is characterized in that described irradiation adopts the energetic ray source to carry out, add in the rubber latex or do not add crosslinking coagent that drying again behind the irradiation obtains fully vulcanized powder rubber.
9. by the described method of claim 7, it is characterized in that described energetic ray source is selected from cobalt source, X-ray, ultraviolet ray and high-energy electron accelerator.
10. by the described method of claim 7, it is characterized in that described energetic ray source is the cobalt source.
11. by the described method of claim 7, it is characterized in that described rubber latex is selected from natural rubber latex, styrene butadiene rubber latex, carboxylic styrene-butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, chloroprene rubber latex, content of polybutadiene rubber latex, esters of acrylic acid rubber latex, vinylpyridiene-styrene-butadiene rubber latex, polyisoprene rubber latex, isoprene-isobutylene rubber latex, ethylene-propylene rubber(EPR) latex, thiorubber latex, Acrylester Butadiene Rubber latex, urethanes latex and fluoroelastomer latex.
12. by the described method of claim 7, it is characterized in that, add crosslinking coagent when irradiation in rubber latex, described crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent, polyfunctional group crosslinking coagent and arbitrary combination thereof.
13. by the described method of claim 12, it is characterized in that, described crosslinking coagent is selected from (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate or Dipentaerythritol five (methyl) acrylate and arbitrary combination thereof.
14., it is characterized in that described drying is carried out spraying drying with spray-dryer or by carrying out with the precipitation desiccating method by the described method of claim 7.
15., it is characterized in that described drying is carried out with spray-dryer by the described method of claim 7.
16., it is characterized in that the dosage of irradiation is 0.1-30Mrad by the described method of claim 7.
17., it is characterized in that the dosage of irradiation is 0.5-20Mrad by the described method of claim 7.
18., it is characterized in that the add-on of described crosslinking coagent is the 0.1-10% of gum weight by the described method of claim 12.
19., it is characterized in that the add-on of described crosslinking coagent is the 0.5-9% of gum weight by the described method of claim 12.
20., it is characterized in that the add-on of described crosslinking coagent is the 0.7-7% of gum weight by the described method of claim 12.
21. by the described method of claim 14, it is characterized in that the inlet temperature of described spray-dryer is 100 ℃-200 ℃, temperature out is 20 ℃-80 ℃.
22. a composition that can be used for preparing toughened plastics or thermoplastic elastomer is characterized in that, it contains each described fully vulcanized powder rubber and plastics of claim 1-6.
23. the described fully vulcanized powder rubber of each of claim 1-6 is used for the application of toughened plastics or preparation thermoplastic elastomer.
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|---|---|---|---|
| CN99125530 | 1999-12-03 | ||
| CN99125530.5 | 1999-12-03 | ||
| PCT/CN2000/000281 WO2001040356A1 (en) | 1999-12-03 | 2000-09-18 | Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof |
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| CN1152082C true CN1152082C (en) | 2004-06-02 |
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