CN101407563A - Method for polarizing polymer - Google Patents
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- CN101407563A CN101407563A CNA2007100358897A CN200710035889A CN101407563A CN 101407563 A CN101407563 A CN 101407563A CN A2007100358897 A CNA2007100358897 A CN A2007100358897A CN 200710035889 A CN200710035889 A CN 200710035889A CN 101407563 A CN101407563 A CN 101407563A
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Abstract
The invention provides a method of polarization of polymer. With ozone used as an oxidant and metal oxide as a catalyst, the polymer and the ozone reacts sufficiently under dynamic or static condition, so as to introduce hydroxyl and/or ester and/or keto-carbonyl and/or carbonyl oxygen-containing polar groups into polymer molecular chains, thus realizing the functionalization to the polymer. The method has the advantages of rapid and highly efficient functionalization of the polymer, no secondary pollution, simple realization to industrialization of polymer producing factories, and therefore the method is a green environmental-friendly method for producing new variety of polymers.
Description
Technical field
The present invention relates to a kind of method of polarizing polymer.
Background technology
The material that high molecular polymer grew up as 20th century, because of its superior over-all properties, comparatively easy moulding process, and wide application field very, and obtained swift and violent development.Non-polar polymeric material PE, PP, PS and SBS, SEBS etc., though be used widely, yet because its surface energy is low, molecule is unreactiveness, causes its cementability, wettability, printing and dyeing property, gas permeability, static resistance and poor with the consistency of other polar polymer, mineral filler etc., cause difficulty of processing to increase, Application Areas is limited.For this reason, the functionalization and modification to non-polar polymer is the heat subject of field of polymer technology always.
At present bibliographical information is more is Study on graft modification to polymkeric substance, as PP being carried out the graft modification of MAH, Feng's sodium etc. (pretreatment process is to the influence of PP solid phase grafting MAH. Feng's sodium, Huang Rui, Li Shujuan, Zhang Zhi forever, Chen Tao. synthetic resins and plastics, 2006,23 (3): 25-27) inquired into uv irradiation method and chemical swelling method pre-treatment influence to the solid Phase Graft of Maleic anhydride onto Polypropylene system.Qi Hongjin etc. (the kinetics of crystallization research of PP grafting MAH. Qi Hongjin, Yang Xiangxin, University Of Qingdao's journal (engineering version), 1998,13 (4): 1-4) also the kinetics of crystallization behind the PP grafting MAH is studied.
To the graft modification of PE, (the research of LDPE solid state mechanochemistry grafting MAH in the pan type physico chemical reactor such as Wang Qi.Chen Huiqiang, Wang Qi.Plastics industry .2000,28 (6): 4-6) studied the pulverizing of HDPE, LDPE, LLDPE and LDPE and the solid state mechanochemistry grafting of degraded and LDPE in the pan-milling.LDPE and maleic anhydride are ground altogether, prepared new LDPE (film grade)-copolymer-maleic anhydride (LDPE-g-MAH), and adopt methods such as IR, DSC and chemistry titration that prepared thing has been carried out analysis and characterization.Kind new grade of bear (research of HDPE solid phase grafting MAH percentage of grafting. Xiong Shanxin, the Geling Hill plum, Zhou Anning. the Xi'an College of Science and Technology journal, 2000,20 (3): be initiator 228-231), prepare high-density polycthylene grafted maleic anhydride (HDPE-g-MAH) with the method for solid state grafting polymerization with benzoyl peroxide (BPO); Detect the generation of graft product with infrared spectroscopy; Calculate percentage of grafting by difference assay.(HDPE chlorination situ-formed graft MAH and product structure Lin Yisheng such as Yin Jinghua, Li Lili, Zhao Jiruo, Yin Jinghua. applied chemistry, 2005,22 (12): 1282-1286) studied with chlorine as the method for initiator to the functionalized grafted with maleic anhydride of high density polyethylene(HDPE) (HDPE) (MAH).Liu Chaozong etc. (Liu Chaozong, Yin Zhihui, Shi Yuping, the research of Yin Zhi brightness .UHMWPE micro mist irradiation grafting MAH. plastics industry, 1997,6:79-82) adopt irradiance method at ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) micro mist surface grafting maleic anhydride (MAH).(LLDPE fusion-grafting MAH functionalization research fourth is red forever for Ding Yonghong, hold NLD, Liu Huaguo opens wind. plastics science and technology, 2001,6:1-5) with the twin screw extruder be reactor, in the presence of radical initiator dicumyl peroxide (DCP), (a spot of methyl-sulphoxide can improve percentage of grafting, suppresses crosslinked to add additive, improve the flowability of grafts), adopt scorification that LLDPE (LLDPE) is carried out maleic anhydride (MAH) grafting.
SBS, SEBS are carried out the graft modification of MAH, external existing matured product Kraton1901 appears on the market, (Zhang Aimin such as Zhang Aimin, Li Chao.Chemical initiation mechanism of maleicanhydride grafted onto styrene-butadiene-styrene block copolymer.EuropeanPolymer Journal.2003,39:1291-1295; Guo Yan, Jiang Yaoming, the research of Zhang Aimin .SEBS fusion-grafting maleic anhydride, polymer material science and engineering .2003,19 (6): 88-91; Jiang Yaoming, Guo Yan, Xu Jianbo, the grafting mechanism of Zhang Aimin .SEBS fusion-grafting MAH, polymer material science and engineering, 2004,20 (9): 97-100; Zhou Lixin, Zhang Aimin, Zhou Tao, the .SEBS grafting MAH technical study of setting a prairie fire in week. elastomerics .2005,15 (6): 23-28; ) from mechanism to the performance, SBS, SEBS grafting MAH have been carried out a large amount of research.Follow the tracks of polypropylene fusion graft process research grafting mechanism by original position FTIR.Also has numerous scholars to SBS, SEBS grafting MAH has carried out studying [[Wu C J.A Kinetic study on grafting of maleic anhydrideonto a thermoplastic elastomer[J] .J Polym Sci Part A Polym Chem, 1993,31:3405.Passaglia E.Grafting of diethyl maleate and maleic anhydride ontostyrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) [J] .Polymer, 2000,41:4389. Feng Dingsong, cross pretty stone, Xie Hongquan. cis-butenedioic anhydrideization synthetic and to compatibilization [J] China Synthetic Rubber Industry of polyoxymethylene/cis-1,4-polybutadiene rubber blend, 1997,20 (1): 37.Wilhelm HM, Felisberti MI, Bulk Modification of styrene-butadiene styrene triblock copolymerwith maleic anhydride[J] .Journal ofApplied Polymer Science, 2000.83 (13): 2953～2960. power, use rare, the Wang Hong GRAFT MODIFICATION OF THERMOPLASTIC ELASTOMER SBS [J] of splashing. the chemical industry journal, 1992,8,43 (4): 506～509. bright, Zhang Yun is bright. maleic anhydride melt grafting and to the toughening effect [J] of nylon 66. and Chinese plastics, 2003,17 (1) Li Gu, Zhang Peiyong, Feng Kaicai, Deng. the synthetic and sign [J] of block SBS grafted maleic anhydride and maleate. plastics industry, 2003, (5): 7～8. seat generation are flat, the synthesis characterization of the flourish .SBS-g.MAH of Li Chun and to the influence [J] of PC/PS co-mixing system consistency. synthetic resins and plastics, 1997, congratulate little China at 14 (2): 19～22., Liu Guisheng, the king likes fine jade .[J]. elastomerics, 1998,8 (4): 12-14. Chen Xu is bright, tight seamark, stone young tiger .[J]. synthetic resins and plastics, 1999,16 (3): the strange .[J of 41-44. Zhu Zhao]. engineering plastics are used, 1996, (1): the 4-7. Ou Yu spring, Cai Weizhen .[J]. the polymer journal, 1991, (3): 301-303.Gonzale E M A, Keskkula H, Paul DR.[J] .Polymer, 1995,36:4605-4618], by fusion or solution graft copolymerization, on the two keys of rubber segments, introduce groups such as COOH, make to have active polar group on the molecular chain, so just improved and fabric, the bonding strength of leather etc.Fusion-grafting is compared with additive method, have realize easily, equipment is simple, advantage of simple technology, but because of its product percentage of grafting is lower, generally is lower than 2%, and MAH is volatile pollutes, so the method for fusion-grafting is still waiting further improvement.Thereby Fu Haiying etc. adopts radiation graft process grafting polar monomer (Fu Haiying, Yu Ming, Xie Leidong, Li Linfan, Yao Si moral .SBS radiation grafting α-Jia Jibingxisuan (MAA) and Determination on content functional polymer journal, 2005,18 (3): 409-413), polymkeric substance exists with the powder solid form in graft reaction like this, and reaction is at room temperature carried out, and side reaction is few, technology is simple, be easy to obtain purified graftomer.(" synthetic resins and plastics " 2003,20 (4): 51-55) studied with twin screw reaction extrusion molding glycidyl methacrylate (GMA) is grafted to SEBS such as king Xiao Lan in addition.
Other study on the modification is also a lot, as SDS, SEBS being carried out polarity end-blocking (EP0743330, CN1676539A, CN1749290A), when anionic polymerisation finishes, add the small amount of polar monomer, continue reaction with polymkeric substance, thereby promote the polarity of polymkeric substance; To the sulfonation modifying of SEBS, SBS (Jiang Ming etc. SCI .1997,18 (2): 309-312. Wei Yi, Chen Wei, Zhao Wenfeng, Li Hao brocade, the sulfonation modifying of Lee Gan .SBS. Speciality Petrochemicals .2002,5:23-25.Liu Dagang, Xie Hongquan, leaf is strong. and sulfonated SBS is from the blend of aggressiveness and crystalline polyolefin. China Synthetic Rubber Industry, 2005,28 (6): 472. Lee laugh at sunshine, Luo Zhiping, Tang Haolin, Yang Jie, Pan Mu. the research of sulfonation SEBS proton exchange membrane prepare and performance. functional materials, 2005,36 (8): 1213-1216), adopt and polystyrene sulfonation similar techniques, the PS section of SEBS or SBS is carried out the contraposition sulfonation modifying; The chloromethylation of SEBS and methylolation (Shen Chong, Zhang Yan, the chloromethylation and the methylolation of thanking to quiet common vetch .SEBS. SCI .1995,20 (5): 827-829) studied chloromethylation and hydroxymethylation on the SEBS phenyl ring; Utilize among the SBS that two keys carry out epoxidation reaction [Hsiue in soft section of the divinyl, G H.Epoxidation of styrene-butadiene-styrene block copolymerand use for gas permeation[J] .J Polym Sci Pt A Polym Chem, 1990,28:3761.WangS M.Epoxidation of partially hydrogenated styrene-butadiene block copolymer usingperacetic acid in a cyclohexane/water heterogeneous system[J] .J Polym Sci Part APolym Chem, 1996,34:1483.Jian X J.Catalytic epoxidation of styrene-butadienetfiblock copolymer with hydrogen peroxide[J] .J Polym Sci Part A Polym Chem, 1991, (29): 1 183.Udipi K.Epoxidation ofstyrene-butadiene block polymers[J] .JAppl Polym Sci, 1979,23:3301～3307. Zhao Long, Mu Ruifeng, the king uses prestige, waits the epoxidation reaction [J] of .SBS. China Synthetic Rubber Industry.1997,20 (2): it is super for 94. Zou, Zhang Yuhong, and He Benqiao waits the epoxidation [J] of .SBS. colloid and polymkeric substance.2000,3 (18): 29～31. to good fortune as, Ma Xingming, Ding Mingshuan, Deng. epoxidation vinyl benzene. the performance study of butadiene block copolymer [J]. rubber industry, 1988,45 (6): 339. Di Ming are big, Ning Zhiqiang, Xu Xiao washes one's hair the epoxidation modification of .SBS and the application in tackiness agent [J] thereof. bonding, 2002,23 (2): 21～23. big monarchs, Di Mingwei, Liu Xiaobo. the development of epoxidation pressure sensitive adhesive [J]. Chinese tackiness agent.2002,11 (3): 28.], can introduce epoxide group therein and carry out modification, thus the polarity of increase SBS, and for further modification and application provide chemical fundamentals.The epoxidation of SBS mainly contains two kinds of methods: a kind of is under the katalysis of transition metal two keys to be oxidized to epoxy group(ing) with oxygen or ozone, and this method catalyzer costliness reclaim difficulty, and reaction yield is low, and advantage is no corrosive medium, and side reaction seldom; It two is with organic peracid two keys to be oxidized to epoxy group(ing), and what wherein have generates peracid with hydrogen peroxide and organic acid reaction, again with the SBS reaction, also have with organic acid and the first mixing of SBS, add hydrogen peroxide again, generate peracid on the spot.Use synthetic peroxy acid in advance, can more effectively two keys be changed into epoxy group(ing), and the side reaction generation is less, but poor stability is a little, and adopt method of in-situ generation, fairly simple, but side reaction is more.These remove the end capped post-modification method of polarity and exist monomer conversion low, and product is easily crosslinked, complex process, shortcomings such as cost height.Though have PP, SEBS grafting MAH and the end capped SBS of vinyl pyridine to appear on the market at present, the production process technology complexity of these products, control difficulty big, on-the-spot global environment pollution are big, the manufacturing cost height.
Ozonation technology has been widely used in water treatment field at present and has been applied in the organic synthesis field.But use it for improve polymer performance report seldom.(the Zhou M (Zhou Mian) of Xuwen group, Fu Y (pay and be lost), XuW (Xuwen) .Studies on ozonizing HDPE[J], Polymer materials science andengineering (polymer material science and engineering), 2004,20 (01): 101-103) realized introducing hydroxyl, ester group, ketone carbonyl, carboxyl and α fast on the molecular chain of high density polyethylene(HDPE) (HDPE) by ozone oxidation, β-unsaturated carboxyl etc. contains the oxygen polar group.(Qiu J (Qiu Jian) in the recent period, Fan P (model duckweed), Xu W (Xuwen), LiuPB (Liu Pengbo) .Ozone treatment of SEBS and toughening PA6 (ozonize of SEBS and the research of toughness reinforcing PA6) Modern Plastics processing and applications (modern plastics processed and applied), 2007,19 (2): 12-14) studied molecular structure and the polar influence thereof of ozonize again, and the toughness reinforcing PA6 of ozonize SEBS is studied to hydrogenated styrene-butadiene-styrene block copolymers (SEBS) product.The result shows, the SEBS pressed powder by ozonize can be on molecular chain the carbonylate oxy radical, and cause that relative molecular mass descends, relative molecular mass distributes and broadens, surface energy improves, polarity increases; Compare with the PA6/SEBS system, the consistency of PA6/ ozonize SEBS system be improved significantly, its shock strength and elongation at break increase substantially.This research has realized a kind of new thought of using the method functionalized polymeric product of environmental protection, but owing to be to adopt the ozonize of finished product pressed powder, the functionalization time is long, and concentrates on solid surface, causes the functionalized degree of depth of this product to be restricted.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polar polymkeric substance of easy, green, environmental protection.
The present invention selects for use the ozone that can be decomposed into oxygen as oxygenant, with the metal oxide is catalyzer, after polymer polymerizing is finished, feed ozone gas in the polymkeric substance continuously and stably, under catalyst action, by stirring or static mixer makes polymkeric substance fully contact, react with ozone, thereby being contained the oxygen polar group, hydroxyl and/or ester group and/or ketone carbonyl and/or carboxyl introduce polymer molecular chain, realization is functionalized to polymkeric substance.
The best place that the present invention realizes is a polymer production factory, and detailed technical scheme is as follows:
Polymkeric substance for solution polymerization or letex polymerization production obtains polymers soln or polymer emulsion after polyreaction is finished, catalyzer is added in this polymers soln or the emulsion; Or the polymkeric substance of producing for mass polymerization, after finishing, polyreaction obtains the polymer body powder, have relatively high expectations or the polymkeric substance of difficult ozonize for degree of functionalization, powder is added in the hydrogen peroxide, for degree of functionalization less demanding be easy to the polymkeric substance of ozonize, powder is added in the entry, make powder fully wetting, add catalyzer again; The add-on of catalyzer is: 0.1g/100g polymkeric substance～5.0g/100g polymkeric substance, feed ozone gas continuously and stably, under stirring or static mixer help, make polymkeric substance follow ozone fully to contact, under 30 ℃～120 ℃ temperature, reacted 4～30 minutes, hydroxyl and/or ester group and/or ketone carbonyl and/or carboxyl are contained the oxygen polar group introduce polymer molecular chain, realize functionalized to polymkeric substance.
Polymkeric substance is non-polar resin or elastomerics, can be polyethylene or polypropylene or polystyrene or butylbenzene SBS Thermoplastic Elastomer or butylbenzene thermoplastic elastomer SEBS or styrene-isoprene thermoplastic elastomer.
Catalyzer is Al
2O
3, TiO
2Powder or organic titanic compound.
In polymers soln or polymer emulsion, add H
2O
2, can improve the speed of polar reaction, H
2O
2Add-on be polymers soln or below 10% of polymer emulsion cumulative volume.
Temperature of reaction can be a room temperature, the highest can be near solvent boiling point, the high reaction effect of temperature is better relatively, generally at 30 ℃～120 ℃.During drop temperature after the polymkeric substance selective polymerization of producing for solution polymerization or letex polymerization is finished, energy is relative with the utilization of time all compare abundant.
The length in reaction times should be determined according to the crosslinked and palliating degradation degree of degree of functionalization and polymer molecule, be generally 4～30 minutes.
Method of the present invention, functionalization of polymers rapidly and efficiently, non-secondary pollution for polymer production factory, only needs to increase by one ozonize operation and just can produce polymkeric substance simultaneously, realizes the functionalized of polymkeric substance, realization of industrialization is quick, and is easy and simple to handle, production cost is low; The gained target product, polar degree height, uniform in quality is stable, does not have the special odor that unconverted monomer brings, and product applications is wide; Method therefor is a kind of method of production polymkeric substance new variety of environmental protection.Catalyst levels needn't separate from polymkeric substance less, and the target product Effect on Performance is not obvious.
Embodiment
Embodiment 1: in band cooling and the 3L four-hole boiling flask that stirs, add 2L hydrogenation reaction terminated SEBS hexanaphthene glue A (YH-504, solid content 11%) not as yet, stir and add 2gTiO down
2, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 18 minutes, gained target product, infrared analysis 3400,1730,1260,110cm
-1At generation oxy radical peak near the place, the product number-average molecular weight drops to 8.3 ten thousand by 140,000, and molecular weight distributing index expands to 1.6 hydroxyl value 240mgKOH/g, acid number 9.8mgKOH/g by 1.1.
Embodiment 2: in the 3L four-hole boiling flask of band cooling and stirring, add the hexanaphthene glue A (solid content 11%) of 2L SEBS, stirring adds 90mlH down
2O
2And 2gTiO
2, divide after being warmed up to 70 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 8 minutes, gained target product, infrared analysis 3400,1730,1260,110cm
-1At generation oxy radical peak near the place, the product number-average molecular weight drops to 5.2 ten thousand by 140,000, and molecular weight distributing index expands to 2.4 hydroxyl value 800mgKOH/g, acid number 12.6mgKOH/g by 1.1.
Embodiment 3: in the 3L four-hole boiling flask of band cooling and stirring, add the hexanaphthene glue liquid B (YH-501, solid content 11%) of 2L SEBS, stirring adds 90mlH down
2O
2And 2gTiO
2, divide after being warmed up to 40 ℃ two mouthfuls to feed ozone and react, ozone flow 1.0L/min, stopped reaction after 30 minutes, gained target product, infrared analysis 3400,1730,1260,110cm
-1At generation oxy radical peak near the place, the product number-average molecular weight drops to 4.2 ten thousand by 100,000, and molecular weight distributing index expands to 2.9 hydroxyl value 660mgKOH/g, acid number 8.6mgKOH/g by 1.1.
Embodiment 4: in the 3L four-hole boiling flask of band cooling and stirring, add the hexanaphthene glue (solid content 11%) of 2LPS, stirring adds 100mlH down
2O
2And 2gTiO
2, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 2.0L/min, stopped reaction after 20 minutes, gained target product, infrared analysis 1735,1685cm
-1At generation oxy radical peak near the place, the product number-average molecular weight drops to 90,000 by 100,000, and molecular weight distributing index expands to 3.9 hydroxyl value 1.3mgKOH/g, acid number 2.9mgKOH/g by 2.5.
Embodiment 5: in the 3L four-hole boiling flask of band cooling and stirring, add the hexanaphthene glue (YH-791h, solid content 17%) of 2L SBS, stirring adds 100mlH down
2O
2And 2gTiO
2, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 15 minutes, gained target product, infrared analysis 1735,1685cm
-1At generation oxy radical peak near the place, the product number-average molecular weight drops to 160,000 by 200,000, and molecular weight distributing index expands to 1.6 hydroxyl value 253mgKOH/g, acid number 6.9mgKOH/g by 1.1.
(the Ba Ling petrochemical industry, PPH-XD-045) 200g adds in the 3L four-hole boiling flask of band cooling and stirring embodiment 6:PP powder, adds 50%H
2O
2All soak to PP, stir and add 2g TiO down
2, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 2.0L/min, stopped reaction after 40 minutes, gained target product, infrared analysis 1730,1100cm
-1At generation oxy radical peak near the place, the product melt flow rate (MFR) is raised to 9g/min by 4g/10min, hydroxyl value 120mgKOH/g, acid number 5.5mgKOH/g.
(the Ba Ling petrochemical industry, PPH-XD-045) 200g adds in the 3L four-hole boiling flask of band cooling and stirring embodiment 7:PP powder, adds 50%H
2O
2All soak to PP, stir and add 0.5g two luxuriant titanium and 2gTiO down
2, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 20 minutes, gained target product, infrared analysis 1730,1100cm
-1At generation oxy radical peak near the place, the product melt flow rate (MFR) is raised to 11g/min by 4g/10min, hydroxyl value 320mgKOH/g, acid number 7.7mgKOH/g.
Embodiment 8:100g LDPE powder adds in the 3L four-hole boiling flask of band cooling and stirring, adds 50%H
2O
2To the whole wetting immersions of PE powder, stir adding 2gAl down
2O
3, divide after being warmed up to 60 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 20 minutes, gained target product, infrared analysis 1730,1100cm
-1At generation oxy radical peak near the place, the product melt flow rate (MFR) is raised to 7g/min by 5g/10min, hydroxyl value 103mgKOH/g, acid number 6.7mgKOH/g.
Embodiment 9:100g LDPE powder adds in the 3L four-hole boiling flask of band cooling and stirring, adds H
2Adding 0.5g two luxuriant titaniums and 2g TiO are down stirred in the whole wetting immersions of O to PE
2, divide after being warmed up to 90 ℃ two mouthfuls to feed ozone and react, ozone flow 1.5L/min, stopped reaction after 30 minutes, gained target product, infrared analysis 1730,1100cm
-1At generation oxy radical peak near the place, the product melt flow rate (MFR) is raised to 9g/min by 5g/10min, hydroxyl value 90mgKOH/g, acid number 3.5mgKOH/g.
Claims (4)
1, a kind of method of polarizing polymer is characterized in that: the polymkeric substance for solution polymerization or letex polymerization production, and after finishing, polyreaction obtains polymers soln or polymer emulsion, catalyzer is added in this polymers soln or the emulsion; Or the polymkeric substance of producing for mass polymerization, after finishing, polyreaction obtains the polymer body powder, have relatively high expectations or the polymkeric substance of difficult ozonize for degree of functionalization, powder is added in the hydrogen peroxide, for degree of functionalization less demanding be easy to the polymkeric substance of ozonize, powder is added in the entry, make powder fully wetting, add catalyzer again; The add-on of catalyzer is: 0.1g/100g polymkeric substance～5.0g/100g polymkeric substance, feed ozone gas continuously and stably, under stirring or static mixer help, make polymkeric substance follow ozone fully to contact, under 30 ℃～120 ℃ temperature, reacted 4～30 minutes, hydroxyl and/or ester group and/or ketone carbonyl and/or carboxyl are contained the oxygen polar group introduce polymer molecular chain, realize functionalized to polymkeric substance.
2, method according to claim 1, it is characterized in that: polymkeric substance is non-polar resin or elastomerics, can be polyethylene or polypropylene or polystyrene or butylbenzene SBS Thermoplastic Elastomer or butylbenzene thermoplastic elastomer SEBS or styrene-isoprene thermoplastic elastomer.
3, method according to claim 1 is characterized in that: catalyzer is Al
2O
3, TiO
2Powder or organic titanic compound.
4, method according to claim 1 is characterized in that: add H in polymers soln or polymer emulsion
2O
2, can improve the speed of polar reaction, H
2O
2Add-on be polymers soln or below 10% of polymer emulsion cumulative volume.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804615A (en) * | 2012-11-06 | 2014-05-21 | 中国石油化工股份有限公司 | Polar diene polymer and preparation method thereof |
| CN106554470A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch |
| CN115057954A (en) * | 2022-05-13 | 2022-09-16 | 华南理工大学 | Ozone-based controllable functionalized polyethylene resin and preparation method thereof |
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| CN1304096C (en) * | 2004-07-02 | 2007-03-14 | 清华大学 | Method for hydrophilic modification of ultrahigh molecular weight polyethylene microporous membrane surface |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804615A (en) * | 2012-11-06 | 2014-05-21 | 中国石油化工股份有限公司 | Polar diene polymer and preparation method thereof |
| CN103804615B (en) * | 2012-11-06 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of polarity diene polymer and preparation method thereof |
| CN106554470A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch |
| CN106554470B (en) * | 2015-09-30 | 2018-12-25 | 中国石油化工股份有限公司 | A method of preparing the Aggregate SBS latex for modified emulsifying asphalt or modified pitch |
| CN115057954A (en) * | 2022-05-13 | 2022-09-16 | 华南理工大学 | Ozone-based controllable functionalized polyethylene resin and preparation method thereof |
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