CN1012734B - Synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymer - Google Patents
Synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymerInfo
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- CN1012734B CN1012734B CN 88102211 CN88102211A CN1012734B CN 1012734 B CN1012734 B CN 1012734B CN 88102211 CN88102211 CN 88102211 CN 88102211 A CN88102211 A CN 88102211A CN 1012734 B CN1012734 B CN 1012734B
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- alpha
- vanadium
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- organosilicon
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Abstract
The present invention provides a method for synthesizing an organosiloxane macromonomer with a stable terminal group structure, and for copolymerizing the organosiloxane macromonomer onto alpha-olefin to obtain an alpha-olefin/organosiloxane graft polymer. The obtained copolymer is used for improving the surface property and the wear-resisting property of some high molecular materials, and the mechanical properties of the high molecular materials are favorably maintained.
Description
The invention relates to the synthetic of end-vinyl siloxane macromer and with the copolymerization of alpha-olefin.
Along with macromolecular material in the application with the relevant occasion of friction such as bearing, artificial skelecton, its surface properties and abrasion resistance properties had been proposed than higher in the past requirement.Because macromolecular material itself does not carry out some modification to it sometimes, just is difficult to reach the performance of expection, thereby has limited the use range of material.How to improve an important topic of the surface property of material and the modification that wear resisting property is macromolecular material, (the Dowcoring of Dow corning company, R, Smith, Plastics Design and Processing, 17(8), 53(1977)) early seventies has been developed with Organosiliconpolymermodified modified macromolecular material (as polystyrene, nylon etc.) surface properties, wear-resisting property.The result shows, the adding of organosilicon polymer can improve the performance of these aspects of corresponding macromolecular material greatly, with the common high molecular materials of this method modification sometimes even can replace expensive lubricating plastic.
But the adding of organosilicon polymer in the surface properties of improving the phase emergencing copolymer and wear-resisting property, also makes the element body mechanical property obviously reduce, and has influenced the use of its reality.Aspect in addition, because organosilicon polymer often by simple blend, even can not get the uniform sample of macroscopic view with the most organic polymer difference of mutual solubility and both melt viscosities not, component stability is also very poor.In order to overcome these shortcomings, with the block or the graft copolymer of oxosilane macromolecular material is carried out modification, be the approach that can explore (D, T Clarke, polymer surfaces, Chemical Industry Press, 1985).Yet, the block of some siloxanes or graft copolymer synthetic, itself has certain degree of difficulty.Block or graft copolymer as alpha-olefin and organo-siloxane.People such as Davies report the method (Brit, 1,376,446(1974)) of coming synthesizing polyethylene-polydimethylsiloxaneblock block copolymers with the method for polyhutadiene section in hydrogenated butadiene polymer-polydimethylsiloxaneblock block copolymers.But gained polyethylene sections fusing point is very low, and intensity is also very poor, is unfavorable for and polyethylene, particularly high density polyethylene(HDPE) blend (Li Weidong, Changchun applied chemistry institute Ph D dissertation, 1987).And can not synthesize other alpha-olefin with aforesaid method, as propylene etc., with the segmented copolymer of organo-siloxane.
The object of the present invention is to provide and a kind ofly synthetic have the organo-siloxane macromonomer of stable end groups structure, then itself and alpha-olefin copolymer are closed the method that obtains the graft copolymerization of alpha-olefine-hydrocarbon/organosilicon oxygen alkane.
Characteristics of the present invention are to use and contain the initiator that two keys are closed in insatiable hunger, and its general formula is H
2C=CHRM(R is the alkane or the phenyl ring of 0 to 5 carbon, and M is a basic metal), as allyl group basic metal, (these monomers can be hexamethyl cyclotrisiloxane (D in initiation organo-siloxane cyclic monomer polymerizations such as vinyl basic metal
3), octamethylcyclotetrasiloxane, 1,3,5-trimethylammonium-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl--Ji 1,3,5,7-tetraphenyl cyclotetrasiloxane), obtain a kind of end-vinyl organopolysiloxane macromonomer.Polymer solvent can be a dioxane, tetrahydrofuran (THF), ether, the mixed solvent body (volume ratio is 1: 99 to 100: 0) of aprotic polar solvent such as methyl-sulphoxide or they and compositions such as alkane or aromatic hydrocarbon.Monomer concentration is 1%～50%.Polymerization temperature is-30 ℃～80 ℃.With gained organo-siloxane macromonomer, in hydro carbons or aromatic hydrocarbon solvent, at vanadium or titanium compound (vanadium oxytrichloride, vanadium trichloride, triacetyl acetone vanadium, titanous chloride, titanium tetrachloride) and AlR
3-yX
yClose with alpha-olefin copolymer in the catalyst system that (R is 2～4 carbon alkyl, and X is a halogen, Y=0～2) formed, can obtain alpha-olefine-hydrocarbon/organosilicon oxygen alkane lopwood multipolymer.Its copolymerization condition is: solvent is hexane, heptane, hydrogenated gasoline, hexanaphthene etc., alpha-olefin can be ethene or propylene, polymer monomer concentration is 0.1%～50%(the best 0.1～10%), catalyst V (Ti)/Al ratio is 1～200, co-polymerization temperature is-80～50 ℃.
Characteristics such as characteristics of the present invention are that the goods of gained behind the alpha-olefine-hydrocarbon/organosilicon oxygen alkane graft copolymer of aforesaid method gained and corresponding poly-(alpha-olefin) homopolymer blend are had more excellent abrasion resistance properties, and product surface is smooth.Compare (when organosilicon polymer content is identical) with poly-(alpha-olefin)/organosilicon polymer simple blend, blend of the present invention has higher abrasion resistance properties and body mechanical property.See Table.
Embodiment 1
Get 10 milliliters of the tetrahydrofuran solutions (concentration is 0.35 mol) of allyl group lithium, be added to D
3Tetrahydrofuran solution in (D
3Weight concentration be/100 milliliters of 20 grams), then 50 ± 1 ℃ of down reactions 7 hours.After the trimethylchlorosilane termination, use methanol extraction.Obtain liquid terminal olefine base-polydimethylsiloxanemacromer macromer.D
3Transformation efficiency be 83%.The macromonomer molecular weight is 8.8 * 10
3Gram/mole.
Embodiment 2
Get 2.5 milliliters of the tetrahydrofuran solutions (concentration is with embodiment 1) of allyl group lithium, be added to D
3Hexanaphthene/tetrahydrofuran (THF) mixed solvent in (D
3Weight concentration be 26 the gram/100 milliliters; The volume ratio of hexanaphthene and tetrahydrofuran (THF) is 4: 1), reacted 7 hours down at 50 ± 1 ℃.After the trimethylchlorosilane termination, use methanol extraction.Obtain liquid end allyl group-polydimethylsiloxanemacromer macromer.D
3Transformation efficiency be 76%, the molecular weight of macromonomer is 17 * 10
3Gram/mole.
Embodiment 3
Get embodiment 2 gained organopolysiloxane macromonomers 1 gram,, feed ethylene gas with 100 moles of hexanaphthene dissolvings.Under 10 ± 1 ℃, inject AlEt successively
2Cl1.1 milliliter (concentration is 0.9 mol) and VOCl
30.19 milliliter (concentration is 0.27 mol), and copolymerization 20 minutes.After ethanol termination polyreaction, filter out solvent.Behind the unreacted macromonomer of cyclohexane solvent stripping, vacuum-drying is to constant weight.Product 4.2 grams; Polysiloxane level is 3.0%; The macromonomer transformation efficiency is 13%.
Embodiment 4
Get embodiment 2 gained organopolysiloxane macromonomers 6 gram, by condition and the ethylene copolymer of embodiment 3 and carry out aftertreatment.Product 3.0 grams, polysiloxane level is 16%; The macromonomer transformation efficiency is 8%.
Embodiment 5
Get 5 parts of embodiment 4 gained polyethylene-polydimethylsiloxane graft copolymer, in Banbury mixer, be mixed under 150 ℃ of the high density polyethylene(HDPE)s 95 parts (Shanghai Gaoqiao chemical plant product, MI=10 Grams Per Minute).The above-mentioned blend of part is molded into convex under 150 ℃, its projection plane specification is 2cm * 2cm.The above-mentioned sample that is molded into is drawn at lattice and carries out abrasion resistance properties on XiLi (Grassley) abrasion machine and measure.Counterpart is that (smooth finish is stainless steel
3), positive pressure is 9 kilograms on every sample, and rotational line speed is 3.3 kilometers/hour.Survey abrasion loss (data are seen attached list) after 27 hours.Other gets the above-mentioned blend of part, in 150 ℃ of counterdie tablet formings, is cut into inferior bell type sample (long 2cm, wide 0.2cm) Instron 1121 type puller system working sample mechanical properties then, and pulling rate is 10 millimeters/minute, and temperature is 25 ± 5 ℃ (data are seen attached list).
Embodiment 6
Getting polydimethylsiloxane content is 13%, and the branched chain molecule amount is with 2.7 parts of the polyethylene of embodiment 5-polydimethylsiloxane graft copolymer, and 97.3 parts of high density polyethylene(HDPE)s are mixed by embodiment 5 conditions.Make the sample bar that length is respectively 3cm * 0.7cm * 0.4cm.With cast iron is counterpart, and velocity of rotation is 400 kilometers/hour, and positive pressure is 15 kilograms.High rotating speed wearability test carries out (data are seen attached list) on the M200 trier.
Reference examples 1
Measure the abrasion resistance properties of pure high density polyethylene(HDPE) and measure mechanical property (data are seen attached list) by embodiment 5 conditions.
Reference examples 2
Measure the polishing machine and the mechanical property (data are seen attached list) of density polyethylene/polydimethylsiloxane blend by embodiment 5 conditions.Wherein the content of polysiloxane in total blend is identical with embodiment 5.
Reference examples 3
Measure the abrasion resistance properties of pure high density polyethylene(HDPE) by embodiment 6 conditions.
Subordinate list blend wear resisting property and mechanical property
Embodiment 5 reference examples 2 reference examples 1 embodiment 6 reference examples 3
Abrasion loss (milligram) 5.0 8.0 14.3 3.7 6.7
Tensile strength (MPa) 25 23 28
Claims (4)
1, the synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymer is characterized in that (general formula is H with the initiator that contains unsaturated double-bond
2C=CHRM, R are the alkane or the benzene hydrocarbon ring of 0 to 5 carbon, and M is a basic metal), cause the polymerization of organo-siloxane cyclic monomer, obtain a kind of end-vinyl organopolysiloxane macromonomer; This monomer is at vanadium or titanium compound (VOCl
3Triacetyl acetone vanadium, vanadium trichloride, titanous chloride, titanium tetrachloride) and AlR
3-yXy (R is a 2-4 carbon alkyl, and X is a halogen, Y=0-2) in the catalyst system of Zu Chenging with alpha-olefine polymerizing, promptly get multipolymer.
2, the synthetic method of organosilicon graft polymer as claimed in claim 1 is characterized in that organo-siloxane ring monomer is the hexamethyl cyclotrisiloxane octamethylcyclotetrasiloxane, 1,3,5-trimethylammonium-1,3,5 triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl--1,3,5,7-tetraphenyl cyclotetrasiloxane.
3, the synthetic method of graft copolymer as claimed in claim 1, when it is characterized in that organosilicon synthesizes end-vinyl organo-siloxane macromole, solvent for use can be a dioxane, tetrahydrofuran (THF), ether, aprotic polar solvents such as dimethyl sulfoxide (DMSO), or the mixed solvent (volume ratio is 1: 99 to 100: 0) of they and compositions such as alkane or aromatic hydrocarbon, polymerization temperature is-30 ℃-80 ℃.
4, the synthetic method of organosilicon graft polymer as claimed in claim 1, it is characterized in that the organo-siloxane macromole is to close with alpha-olefin copolymer in the catalyst system of vanadium or titanium compound and aluminum alkyls (or chlorination aluminum alkyls) composition, used solvent is hexane, heptane, gasoline hexanaphthene during copolymerization, vanadium (or titanium)/Al ratio is 1 to 200, co-polymerization temperature is-and 80-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102211 CN1012734B (en) | 1988-04-13 | 1988-04-13 | Synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102211 CN1012734B (en) | 1988-04-13 | 1988-04-13 | Synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036963A CN1036963A (en) | 1989-11-08 |
| CN1012734B true CN1012734B (en) | 1991-06-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102211 Expired CN1012734B (en) | 1988-04-13 | 1988-04-13 | Synthetic method of alpha-olefine-hydrocarbon/organosilicon graft polymer |
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| CN102532428B (en) * | 2011-12-31 | 2013-06-05 | 浙江大学 | Nano-grade TiO2/silicone-acrylate core-shell composite emulsion and preparation method thereof |
| CN113845809B (en) * | 2021-10-10 | 2022-04-15 | 山立欣业新材料(广东)有限公司 | Cleaning-free antirust material capable of being stripped or cleaned by heating as well as preparation and application thereof |
| CN117050318B (en) * | 2023-10-10 | 2023-12-19 | 络合高新材料(上海)有限公司 | Modified saturated carbon ring type epoxy resin and preparation method and application thereof |
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1988
- 1988-04-13 CN CN 88102211 patent/CN1012734B/en not_active Expired
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| CN1036963A (en) | 1989-11-08 |
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