CN102295731A - Graft modified styrene thermoplastic elastomer and preparation method thereof - Google Patents
Graft modified styrene thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graft modified styrene thermoplastic elastomer, including a main chain and a grafted chain. The main chain is a segmented copolymer from copolymerization of styrene and alkene; and the grafted chain is a grafted chain from reactions of an N-vinyl compound and a grafting monomer with the main chain; the graft modified styrene thermoplastic elastomer has a grafting rate of 2-4.5%; and a styrene block content accounts for 10-60wt% in the segmented copolymer. According to the invention, the N-vinyl compound rich in electrons is used as an auxiliary grafting monomer in order to increase grafting reaction sites or activity of the objective grafting monomer and enhance the grafting rate. The invention also provides a preparation method of the modified styrene thermoplastic elastomer.
Description
Technical field
The present invention relates to polymkeric substance and preparation field thereof, be specifically related to a kind of graft modification styrene analog thermoplastic elastomer and preparation method thereof.
Background technology
Styrene analog thermoplastic elastomer is the elastomer material of a class excellent property, and it has nontoxic, good toughness, tension set is little and be easy to advantages such as processing.Typical styrene analog thermoplastic elastomer molecular chain is made up of two ends vinylbenzene section, middle polyolerin elastomer section three blocks.Early stage synthetic styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), its rubber segments contains unsaturated double-bond, so thermotolerance, tensile strength, ageing resistance and wear resisting property etc. are not as synthetic rubber.Hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymer by hydrotreatment unsaturated rubber section and have the vinylbenzene-iso-butylene-styrene block copolymer (can be referred to as the saturation type styrene analog thermoplastic elastomer) of saturated rubber segment structure, the rubber segments that obviously is better than its shock strength, thermotolerance and heat-resistant aging etc. contains the styrene analog thermoplastic elastomer of two keys, and the good reputation of " the 4th generation rubber " is in the industry cycle arranged.
2007, global styrene analog thermoplastic elastomer throughput surpassed 1,750,000 tons, and annual speed with 4.8% is increasing.Except using as elastomerics, styrene analog thermoplastic elastomer also is widely used as expanding material, toughner, thin film adhesion layer and metal bond material.Yet, styrene analog thermoplastic elastomer is a non-polar material, because its non-polar character, its surfactivity is low, wetting ability, dyeability, cohesiveness, static resistance are poor, therefore not only very poor with the consistency of many macromolecular materials or mineral filler, and its use properties as expanding material, toughner, thin film adhesion layer and metal bond material also has been subjected to certain influence.
The researchist solves the above-mentioned shortcoming that styrene analog thermoplastic elastomer exists by introduce groups such as acid anhydrides, epoxide group, sulfonic group, carboxyl, ester group on its molecular chain.At present, the graft modification of styrene analog thermoplastic elastomer mainly contains two kinds of methods: solution graft copolymerization and fusion-grafting.Chinese patent ZL200310107941.7 discloses a kind of maleic anhydride graft styrene-butadiene-styrene block copolymer solvent process for thermosynthesizing, and this method is simple, can obtain higher percentage of grafting.Bibliographical information be initiator with the dibenzoyl peroxide, in toluene solution to the hydrogenated styrene-butadiene-styrene block copolymers graft acrylic acid, the graftomer of preparation is especially suitable for use as tackiness agent [Liu Chengmei, Zheng Lunsheng, the synthesis and structure analysis of SEBS-acrylic acid graft copolymer, polymer material science and engineering, 2003,19 (5): 54-57].The solution graft copolymerization long reaction time, grafting efficiency is low, need to consume poisonous in a large number, flammable solvent, and solvent recuperation is expensive big, the cost height, serious to the human injury, contaminate environment, and this class methods occupation of land is big, and the production cost height is difficult to realize continuous operation.Based on the fusion-grafting that reaction is extruded, raw material metering, conveying, mixing, reaction and product processing is integrated, thus realized serialization production, simplified technical process, reduced the reaction times, reduced production cost, be fit to scale operation.Bibliographical information the fusion-grafting legal system maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymers [week sets a prairie fire, Zhou Weiping, MAH modification SEB S Performance Influence Factor is inquired into, elastomerics, 2009,19 (3): 57-59] of saddling a horse for riding.Bibliographical information in Bradley Bender Banbury mixer, carry out the fusion-grafting research [E.Passaglia of the maleic anhydride of hydrogenated styrene-butadiene-styrene block copolymers and derivative thereof, S.Ghetti, F.Picchioni, G.Ruggeri, Grafting of diethyl maleate and maleic anhydride onto styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS), Polymer, 2000,41:4389-4400].It is that monomeric percentage of grafting and grafting efficiency are not high that there is maximum shortcoming in fusion-grafting, and the graft modification effect has much room for improvement.In order to solve fusion-grafting percentage of grafting, a difficult problem that grafting efficiency is low, the researchist has invented vinylbenzene and derivative thereof the auxiliary crosslinking technology as auxiliary grafting agent.U.S. Pat 4857254 discloses styrenic derivatives such as vinylbenzene, 2-methyl styrene as auxiliary grafting agent, improves the fusion-grafting method of monomer-grafted rates such as maleic anhydride, itaconic anhydride, citraconic anhydride.
Yet, for the styrene analog thermoplastic elastomer material, in the grafting process, have the active free radical of grafting and mainly be created on the alkene segment, the vinylbenzene or derivatives thereof but is dispersed in the vinylbenzene segment phase region, causes the free radical on vinylbenzene or derivatives thereof and the alkene segment to be difficult to come in contact, can not form the macromolecular radical of vinylbenzene or derivatives thereof, and do not have auxiliary grafting effect, cause percentage of grafting to improve, the poor performance of styrene analog thermoplastic elastomer.[E.Passaglia，S.Ghetti，F.Picchioni，G.Ruggeri，Grafting?of?diethyl?maleate?and?maleic?anhydride?onto?styrene-b-(ethylene-co-1-butene)-b-styrene?triblock?copolymer(SEBS)，Polymer，2000，41：4389-4400；Sara?Filippi，Hristo?Yordanov，Liliya?Minkova，Giovanni?Polacco，Marco?Talarico，Reactive?compatibilizer?precursors?for?LDPE/PA6?blends，maleic?anhydride?and?glycidyl?methacrylate?grafted?SEBS，Macromolecular?Materials?and?Engineering，2004，289，512-523]。
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of graft phenylethene analog thermoplastic elastomer and preparation method thereof.Improve described graft modification styrenic thermoplastic elastomer's percentage of grafting.
In order to solve the prior art problem, the invention provides a kind of graft modification styrene analog thermoplastic elastomer, comprise main chain and grafted chain; Described main chain is the segmented copolymer that obtains after vinylbenzene and the olefin-copolymerization reaction, and described grafted chain is the grafted chain that obtains after N-vinyl compound and grafted monomer and the main chain reaction; The percentage of grafting of described graft modification styrene analog thermoplastic elastomer is 2%～4.5%; The content of styrene block is 10wt%～60wt% in the described segmented copolymer.
Preferably, described segmented copolymer is: styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene segmented copolymer, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-isoprene-styrene block copolymer, in vinylbenzene-iso-butylene segmented copolymer and the vinylbenzene-iso-butylene-styrene block copolymer one or more.
Preferably, described N-vinyl compound is one or more in N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole and the N-vinyl imidazole.
Preferably, described grafted monomer is one or more in maleic anhydride, dibutyl maleinate, itaconic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl isobutyrate, Sodium styrene sulfonate, vinyl cyanide, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylformic acid list macrogol ester and the methacrylic acid.
The present invention also provides a kind of graft modification process for preparing thermoplastic phenylethylene elastomer, comprising:
A) segmented copolymer, N-vinyl compound, the grafted monomer that obtains after the reaction of vinylbenzene and olefin-copolymerization mixed pre-irradiation afterwards, obtain compound;
Graft reaction takes place in the compound melting mixing that b) step a) is obtained, and obtains the graft modification styrene analog thermoplastic elastomer.
Preferably, described N-vinyl compound and grafted monomer is (1～15) by weight: (2～20).
Preferably, described N-vinyl compound is one or more in N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole and the N-vinyl imidazole.
Preferably, described grafted monomer is one or more in maleic anhydride, dibutyl maleinate, itaconic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl isobutyrate, Sodium styrene sulfonate, vinyl cyanide, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylformic acid list macrogol ester and the methacrylic acid.
The present invention also provides a kind of graft modification process for preparing thermoplastic phenylethylene elastomer, comprising:
N) segmented copolymer, N-vinyl compound, grafted monomer, the initiator that obtains after the reaction of vinylbenzene and olefin-copolymerization obtained compound after mixing;
M) with step n) graft reaction, take place and obtain the graft modification styrene analog thermoplastic elastomer in the compound melting mixing that obtains.
Preferably, described initiator is: one or more in dicumyl peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, peroxidation butyl ether and the peroxidation di-t-butyl.
The invention provides a kind of graft modification styrene analog thermoplastic elastomer, comprise main chain and grafted chain; Described main chain is the segmented copolymer that obtains after vinylbenzene and the olefin-copolymerization reaction, and described grafted chain is the grafted chain that obtains after N-vinyl compound and grafted monomer and the main chain reaction; The percentage of grafting of described graft modification styrene analog thermoplastic elastomer is 2%～4.5%; The content of styrene block is 10wt%～60wt% in the described segmented copolymer.Graft modification styrene analog thermoplastic elastomer provided by the invention uses and is rich in the N-vinyl compound of electronics as electron donor, carry out graft reaction with the N-vinyl compound as auxiliary grafted monomer, increase the graft reaction site or the activity of described grafted monomer, improved percentage of grafting.
The present invention also provides two kinds of preparation methods, used irradiation method and initiator method on main chain, to form free radical respectively, melting mixing by compound carries out graft reaction then, and preparation method provided by the invention is simple to operate, is fit to large-scale industrial production.
Description of drawings
Auxiliary grafted monomer of the use that Fig. 1 embodiment of the invention provides and the styrene analog thermoplastic elastomer infrared spectrum contrast of not using auxiliary grafted monomer;
The nucleus magnetic hydrogen spectrum of the styrene analog thermoplastic elastomer of the auxiliary glycidyl methacrylate graft of the N-vinyl pyrrolidone that Fig. 2 embodiment of the invention 1 provides.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that just restriction of these descriptions for further specifying the features and advantages of the present invention rather than patent of the present invention being required.
The invention provides a kind of graft modification styrene analog thermoplastic elastomer, comprise main chain and grafted chain; Described main chain is the segmented copolymer that obtains after vinylbenzene and the olefin-copolymerization reaction, and described grafted chain is the grafted chain that obtains after N-vinyl compound and grafted monomer and the main chain reaction; The percentage of grafting of described graft modification styrene analog thermoplastic elastomer is 2%～4.5%; The content of styrene block is 10wt%～60wt% in the described segmented copolymer.
According to the present invention, described segmented copolymer is styrene analog thermoplastic elastomer, owing to be to use vinylbenzene and olefin-copolymerization, so hard section is a vinylbenzene, and soft section be alkene.Usually, other functionalization groups of grafting the time, the site of graft reaction often is on soft section, because problems such as sterically hindered and free-radical generating difficulty have limited percentage of grafting, makes the styrene analog thermoplastic elastomer after the modification not reach expected effect.According to the present invention, described styrenic block copolymer is preferably styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene segmented copolymer, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-isoprene-styrene block copolymer, in vinylbenzene-iso-butylene segmented copolymer and the vinylbenzene-iso-butylene-styrene block copolymer one or more.
According to the present invention, described N-vinyl compound is the compound that is rich in electronics, exists as electron donor, improves the reactive behavior on the styrene block phenyl ring, makes can generate free radical on described hard section, increases reaction site.According to the present invention, described N-vinyl compound is preferably one or more in N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole and the N-vinyl imidazole.
The grafted monomer that the present invention uses is preferably anhydrides, contains the compound and the acrylic compounds of two keys, more preferably one or more in maleic anhydride, dibutyl maleinate, itaconic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl isobutyrate, Sodium styrene sulfonate, vinyl cyanide, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylformic acid list macrogol ester and the methacrylic acid.These grafted monomer can bring different performances and more reaction site to styrene analog thermoplastic elastomer, are twice-modified laying the groundwork from now on.
The present invention also provides a kind of graft modification process for preparing thermoplastic phenylethylene elastomer, comprising: a) segmented copolymer, N-vinyl compound, the grafted monomer that obtains after the reaction of vinylbenzene and olefin-copolymerization mixed pre-irradiation afterwards, obtain compound;
Graft reaction takes place in the compound melting mixing that b) step a) is obtained, and obtains the graft modification styrene analog thermoplastic elastomer.
The present invention also provides a kind of graft modification process for preparing thermoplastic phenylethylene elastomer, comprising: n) segmented copolymer, N-vinyl compound, grafted monomer, the initiator that obtains after the reaction of vinylbenzene and olefin-copolymerization obtained compound after mixing;
M) with step n) graft reaction, take place and obtain the graft modification styrene analog thermoplastic elastomer in the compound melting mixing that obtains.
According to the present invention, described graft modification process for preparing thermoplastic phenylethylene elastomer is specially: the first step: the raw material mechanically mixing
To the graft reaction system that pre-irradiation causes, its process is: after styrene analog thermoplastic elastomer is carried out the pre-irradiation processing with electron beam or gamma-rays, mix 2-8min with auxiliary grafting agent, grafted monomer in high-speed mixer and obtain compound; By weight, auxiliary grafting agent consumption is the 1-15wt% of styrene analog thermoplastic elastomer total amount, and the grafted monomer consumption is the 2-20wt% of styrene analog thermoplastic elastomer total amount.
To the graft reaction system that adopts initiator to cause, its process is: will assist grafting agent, grafted monomer, initiator, styrene analog thermoplastic elastomer to mix 2-8min in high-speed mixer and obtain compound; By weight, auxiliary grafting agent consumption is the 1-15wt% of styrene analog thermoplastic elastomer total amount, the grafted monomer consumption is the 2-20wt% of styrene analog thermoplastic elastomer total amount, and initiator amount is the 0.02-1.5wt% of styrene analog thermoplastic elastomer total amount.
Described electron beam or gamma-rays carry out pre-irradiation to be handled, and it is characterized in that: electron beam is irradiation source with the rumbatron, and irradiation dose is 2-50kGy; Gamma-rays is with Co
60Be irradiation source, irradiation dose is 2-30kGy.
According to the present invention, in the described segmented copolymer vinylbenzene segment weight content be preferably be 10-60wt%, melt flow rate (MFR) be 0.1-40.0g/10min (200 ℃, 5.0Kg).
Described initiator is preferably one or more in dicumyl peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, peroxidation butyl ether and the peroxidation di-t-butyl.
Second step: the fusion-grafting in twin screw extruder
The compound that the first step is obtained is sent into and is carried out fusion-grafting in the twin screw extruder, and the design temperature of forcing machine is 140-215 ℃, and head temperature is 155-205 ℃, and the residence time of material in forcing machine is 1.0-8.0min.The material of extruding is after pelletizing, dissolving precipitated method purification and drying, and sealing is at room temperature preserved.
Provided by the invention kind of styrene analog thermoplastic elastomer grafts polar group content height, color is light, good mechanical performance.Be suitable as toughner, expanding material, thin film adhesion layer and metal bond material etc.
Below in conjunction with embodiment, the present invention further to be set forth, scope of the present invention is not limited only to these embodiment.The technical parameter of the styrene analog thermoplastic elastomer that embodiment is used sees table 1 for details.
The technical parameter of the styrene analog thermoplastic elastomer that table 1 embodiment, comparative example use
* MFR, melt flow rate (MFR), with reference to GB GB/T3682, test condition is 200 ℃, 5.0Kg.
50 kilograms of A1 powders are handled with the electron beam pre-irradiation, irradiation dose 4kGy, then with 1.2 kilograms of N-vinyl pyrrolidones, 3.3 kilograms of glycidyl methacrylate in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 160-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A1 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 1
50 kilograms of A1 powders are handled with the electron beam pre-irradiation, irradiation dose 4kGy, then with 3.3 kilograms of glycidyl methacrylate in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 160-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A1 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
50 kilograms of A2 powders are handled with the gamma-rays pre-irradiation, irradiation dose 2kGy, then with 1.2 kilograms of N-caprolactams, 2.5 kilograms of maleic anhydrides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 160-195 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A2 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 2
50 kilograms of A2 powders are handled with the gamma-rays pre-irradiation, irradiation dose 2kGy, then with 2.5 kilograms of maleic anhydrides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 160-195 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A2 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
With 50 kilograms of A3 powders and 1.0 kilograms of N-vinylcarbazole, 3.2 kilograms of glycidyl isobutyrates, 15 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-195 ℃ along charging opening to heading temperature, head temperature is 175-185 ℃, and the residence time of A3 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 3
With 50 kilograms of A3 powders and 3.2 kilograms of glycidyl isobutyrates, 15 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-195 ℃ along charging opening to heading temperature, head temperature is 175-185 ℃, and the residence time of A3 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
With 50 kilograms of A4 powders and 1.0 kilograms of N-vinyl imidazoles, 3.0 kilograms of vinylformic acid list macrogol esters, 18 gram peroxidation butyl ethers in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A4 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 4
With 50 kilograms of A4 powders and 3.0 kilograms of vinylformic acid list macrogol esters, 18 gram peroxidation butyl ethers in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A4 powder in forcing machine is 2.0-3.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
50 kilograms of A5 powders are handled with the electron beam pre-irradiation, irradiation dose 8kGy, then with 1.4 kilograms of N-vinyl pyrrolidones, 3.3 kilograms of methyl methacrylates in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A5 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 5
50 kilograms of A5 powders are handled with the electron beam pre-irradiation, irradiation dose 8kGy, then with 3.3 kilograms of methyl methacrylates in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A5 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
With 50 kilograms of A6 powders and 1.0 kilograms of N-vinyl pyrrolidones, 3.1 kilograms of vinylformic acid list macrogol esters, 35 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A6 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 6
With 50 kilograms of A6 powders and 3.1 kilograms of vinylformic acid list macrogol esters, 35 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A6 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
50 kilograms of A7 powders are handled with the electron beam pre-irradiation, irradiation dose 9kGy, then with 1.0 kilograms of N-vinyl imidazoles, 2.8 kilograms of vinyl cyanide in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A7 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 7
50 kilograms of A7 powders are handled with the electron beam pre-irradiation, irradiation dose 9kGy, then with 2.8 kilograms of vinyl cyanide in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A7 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
With 50 kilograms of A8 powders and 1.2 kilograms of N-caprolactams, 2.5 kilograms of Sodium styrene sulfonate, 28 gram isopropyl benzene hydroperoxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 160-195 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A8 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 8
With 50 kilograms of A8 powders and 2.5 kilograms of Sodium styrene sulfonate, 28 gram isopropyl benzene hydroperoxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 160-195 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A8 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
Embodiment 9
50 kilograms of A9 powders are handled with the gamma-rays pre-irradiation, irradiation dose 2kGy, then with 0.8 kilogram of N-vinyl imidazole, 2.0 kilograms of citraconic anhydrides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A9 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 9
50 kilograms of A9 powders are handled with the gamma-rays pre-irradiation, irradiation dose 2kGy, then with 2.0 kilograms of citraconic anhydrides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A9 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
Embodiment 10
With 50 kilograms of A10 powders and 1.3 kilograms of N-vinyl pyrrolidones, 2.6 kilograms of glycidyl isobutyrates, 25 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A10 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 10
With 50 kilograms of A10 powders and 2.6 kilograms of glycidyl isobutyrates, 25 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-200 ℃ along charging opening to heading temperature, head temperature is 180-190 ℃, and the residence time of A10 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
Embodiment 11
With 50 kilograms of A11 powders and 1.0 kilograms of N-vinylcarbazole, 3.4 kilograms of dibutyl maleinates, 37 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-195 ℃ along charging opening to heading temperature, head temperature is 175-185 ℃, and the residence time of A11 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 11
With 50 kilograms of A11 powders and 3.4 kilograms of dibutyl maleinates, 37 gram dicumyl peroxides in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-195 ℃ along charging opening to heading temperature, head temperature is 175-185 ℃, and the residence time of A11 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
Embodiment 12
With 50 kilograms of A12 powders and 0.8 kilogram of N-vinyl imidazole, 3.8 kilograms of glycidyl methacrylate, 18 gram peroxidation butyl ethers in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A12 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 2, and table 2 is the performance index of the styrene analog thermoplastic elastomer grafts of embodiment of the invention preparation.
Comparative example 12
With 50 kilograms of A12 powders and 3.8 kilograms of glycidyl methacrylate, 18 gram peroxidation butyl ethers in high-speed mixer behind the mechanically mixing 3-5min, add fusion-grafting in the response type twin screw extruder, the screw diameter of forcing machine is 40mm, length-to-diameter ratio is 36, setting forcing machine is 165-190 ℃ along charging opening to heading temperature, head temperature is 175-190 ℃, and the residence time of A12 powder in forcing machine is 3.0-5.0min; Graft product through head extrude, pelletizing, dissolution precipitation are purified, after the drying, make the styrene analog thermoplastic elastomer grafts.
Described styrene analog thermoplastic elastomer grafts is carried out performance test, and the result is referring to table 3, and table 3 is the performance index of the styrene analog thermoplastic elastomer grafts of comparative example preparation of the present invention.
Table 2, table 3 have provided the styrene analog thermoplastic elastomer grafts performance that the embodiment of the invention, comparative example prepare respectively.Wherein, the grafted monomer percentage of grafting adopts infrared spectroscopic determination; Melt flow rate (MFR) MFR is with reference to GB GB/T3682, and test condition is 200 ℃, 5.0Kg; Transmittance and mist degree are measured with reference to GB GB3140; Tensile strength and elongation at break are measured with reference to GB GB1040.
The styrene analog thermoplastic elastomer grafts performance of table 2 embodiment of the invention preparation
The styrene analog thermoplastic elastomer grafts performance of table 3 comparative example preparation of the present invention
From table 2 and table 3 as can be seen,, make monomeric pair of key of electron deficiency be rich in electronics, increase its graft reaction activity because electron rich N-vinyl compound can form charge-transfer complex with electron deficiency monomer (as: maleic anhydride); On the other hand, combined with radical velocity ratio grafted monomer (as: glycidyl methacrylate) is faster on electron rich N-vinyl compound and the macromolecular chain, it at first is grafted on the macromolecular chain, and as intermediary and grafted monomer polymerization, thereby the percentage of grafting of raising grafted monomer.Therefore, among the embodiment graft monomer contents of styrene analog thermoplastic elastomer grafts all apparently higher than corresponding comparative example.
Fig. 1 is auxiliary glycidyl methacrylate graft infrared spectrogram.Wherein (a) is hydrogenated styrene-butadiene-styrene block copolymers, (b) be the hydrogenated styrene-butadiene-styrene block copolymers graft glycidyl methacrylate, (c) be the auxiliary glycidyl methacrylate graft hydrogenated styrene-butadiene-styrene block copolymers of N-vinyl pyrrolidone.1730cm among the figure
-1The peak is the carbonyl absorption peak on the glycidyl methacrylate, and as can be seen, the most auxiliary grafted monomer of N-vinyl pyrrolidone can obviously improve the percentage of grafting of glycidyl methacrylate.
For the styrene analog thermoplastic elastomer A1-A4 material of embodiment and comparative example use, its rubber segments contains a large amount of unsaturated double-bonds, so easily crosslinked in the polypropylene fusion graft process, and descending all appears in MFR.Because the use of N-vinyl compound among the embodiment, suppressed crosslinked action effectively, therefore MFR descends lessly, and the styrene analog thermoplastic elastomer grafts occurs then very significantly that MFR descends in the comparative example, even occurs that melt does not flow and the phenomenon that can not test MFR.The transmittance of styrene analog thermoplastic elastomer grafts, mist degree, elongation at break all are better than corresponding comparative example among the embodiment.The elongation at break of styrene analog thermoplastic elastomer grafts obviously descends in the comparative example, has lost elastomeric character substantially, no longer is suitable as to make toughner, expanding material, thin film adhesion layer and metal bond material etc.
For the styrene analog thermoplastic elastomer A5-A12 material of embodiment and comparative example use, its rubber segments does not contain unsaturated double-bond substantially, easily degraded in the polypropylene fusion graft process, and rising all appears in MFR.Because the use of N-vinyl compound among the embodiment, suppressed Degradation effectively, therefore the MFR rising is less, and very significantly MFR rising then appears in the styrene analog thermoplastic elastomer grafts in the comparative example, even can not detect MFR because melt flow rate (MFR) is too big.The transmittance of styrene analog thermoplastic elastomer grafts, mist degree, tensile strength, elongation at break all are better than corresponding comparative example among the embodiment.The tensile strength of styrene analog thermoplastic elastomer grafts, elongation at break obviously descend in the part comparative example, have lost its elastomeric character, no longer are suitable as and make toughner, expanding material, thin film adhesion layer and metal bond material etc.
More than a kind of graft modification styrene analog thermoplastic elastomer provided by the invention and preparation method thereof is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a graft modification styrene analog thermoplastic elastomer is characterized in that, comprises main chain and grafted chain; Described main chain is the segmented copolymer that obtains after vinylbenzene and the olefin-copolymerization reaction, and described grafted chain is the grafted chain that obtains after N-vinyl compound and grafted monomer and the main chain reaction; The percentage of grafting of described graft modification styrene analog thermoplastic elastomer is 2%～4.5%; The content of styrene block is 10wt%～60wt% in the described segmented copolymer.
2. graft modification styrene analog thermoplastic elastomer according to claim 1, it is characterized in that described segmented copolymer is: styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene segmented copolymer, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-isoprene-styrene block copolymer, in vinylbenzene-iso-butylene segmented copolymer and the vinylbenzene-iso-butylene-styrene block copolymer one or more.
3. graft modification styrene analog thermoplastic elastomer according to claim 1 is characterized in that, described N-vinyl compound is one or more in N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole and the N-vinyl imidazole.
4. graft modification styrene analog thermoplastic elastomer according to claim 1, it is characterized in that described grafted monomer is one or more in maleic anhydride, dibutyl maleinate, itaconic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl isobutyrate, Sodium styrene sulfonate, vinyl cyanide, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylformic acid list macrogol ester and the methacrylic acid.
5. a graft modification process for preparing thermoplastic phenylethylene elastomer is characterized in that, comprising:
A) segmented copolymer, N-vinyl compound, the grafted monomer that obtains after the reaction of vinylbenzene and olefin-copolymerization mixed pre-irradiation afterwards, obtain compound;
Graft reaction takes place in the compound melting mixing that b) step a) is obtained, and obtains the graft modification styrene analog thermoplastic elastomer.
6. preparation method according to claim 5 is characterized in that, described N-vinyl compound and grafted monomer by weight being (1～15): (2～20).
7. preparation method according to claim 5 is characterized in that, described N-vinyl compound is one or more in N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole and the N-vinyl imidazole.
8. preparation method according to claim 5, it is characterized in that described grafted monomer is one or more in maleic anhydride, dibutyl maleinate, itaconic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl isobutyrate, Sodium styrene sulfonate, vinyl cyanide, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylformic acid list macrogol ester and the methacrylic acid.
9. a graft modification process for preparing thermoplastic phenylethylene elastomer is characterized in that, comprising:
N) segmented copolymer, N-vinyl compound, grafted monomer, the initiator that obtains after the reaction of vinylbenzene and olefin-copolymerization obtained compound after mixing;
M) with step n) graft reaction, take place and obtain the graft modification styrene analog thermoplastic elastomer in the compound melting mixing that obtains.
10. preparation method according to claim 9 is characterized in that, described initiator is: one or more in dicumyl peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, peroxidation butyl ether and the peroxidation di-t-butyl.
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