CN100368472C - A method for improving the fluidity of polypropylene melt - Google Patents
A method for improving the fluidity of polypropylene melt Download PDFInfo
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- CN100368472C CN100368472C CNB2005100306179A CN200510030617A CN100368472C CN 100368472 C CN100368472 C CN 100368472C CN B2005100306179 A CNB2005100306179 A CN B2005100306179A CN 200510030617 A CN200510030617 A CN 200510030617A CN 100368472 C CN100368472 C CN 100368472C
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 61
- -1 polypropylene Polymers 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 42
- 238000001746 injection moulding Methods 0.000 claims abstract description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims abstract 4
- 150000003077 polyols Chemical class 0.000 claims abstract 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000006254 rheological additive Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 14
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种提高聚丙烯熔体流动性的方法，其采用如下步骤：1)在有机溶剂中和140-220℃下，多元醇、对苯二甲酸酯在催化剂催化下反应获得超支化聚合物；2)将上述制备的超支化聚合物和聚丙烯在150-280℃下经过双螺杆挤出机共混造粒获得高含量超支化聚合物的聚丙烯母粒；或者3)将上述制备的具有高含量超支化聚合物的聚丙烯母粒按照1-100%的重量比与聚丙烯混合后进行注塑成型加工获得含有超支化聚合物的聚丙烯。本发明的方法可以将超支化聚合物作为聚丙烯的流变改性剂，获得含有超支化聚合物的聚丙烯。可以在不改变聚丙烯树脂分子量及其分布的情况下，大大提高聚丙烯的熔体流动性。具有工艺简单、可降低能耗、降低生产成本等特点。The invention relates to a method for improving the fluidity of polypropylene melt, which adopts the following steps: 1) in an organic solvent and at a temperature of 140-220°C, polyols and terephthalate react under the catalysis of a catalyst to obtain hyperbranched polymer; 2) blending and granulating the hyperbranched polymer and polypropylene prepared above through a twin-screw extruder at 150-280° C. to obtain a polypropylene masterbatch with a high content of hyperbranched polymer; or 3) combining the above The prepared polypropylene masterbatch with high content of hyperbranched polymer is mixed with polypropylene according to the weight ratio of 1-100%, and then subjected to injection molding processing to obtain the polypropylene containing hyperbranched polymer. The method of the invention can use the hyperbranched polymer as the rheology modifier of polypropylene to obtain the polypropylene containing the hyperbranched polymer. The melt fluidity of polypropylene can be greatly improved without changing the molecular weight and distribution of polypropylene resin. The invention has the characteristics of simple process, energy consumption reduction, production cost reduction and the like.
Description
Technical field
The invention provides and improve polyacrylic fluidity of molten, reduction machine-shaping method of temperature.With the hyper-branched polyester of ester-interchange method preparation and polypropene blended after, can improve polyacrylic fluidity of molten.Present method has that technology is simple, capable of reducing energy consumption, characteristics such as reduce production costs.
Background technology
Polypropylene (PP) plastics have good temperature resistance, erosion resistance, electrical insulating property because of it, and density is low, cost of material is cheap in addition, the source is abundant, make its throughput, output obtain swift and violent development, can be widely used in the fields such as industry, automobile, tame electrical article, fiber in the last few years.And along with the polyacrylic development of China, its application structure will move closer to level of developed countries, the injection grade polypropylene that is used for industry, automobile, tame electrical article will rise appreciably, the demand of fibrous polypropylene, household electrical appliance PP Pipe Compound, automobile special material will have bigger growth, and the ratio of woven bag consumption will descend.Polypropylene fiber and non-woven fabrics will be a market of China's acrylic resin development potentiality maximum simultaneously, and the consumption aspect medical and health increases and will increase significantly.Because the continuous expansion of polypropylene Application Areas, the polypropylene market of China are in still at present that supply falls short of demand state, breach is bigger, and import volume is in recent years all more than 1,000,000 tons/year.
High workability copolymerization PP is a kind of novel high polymer material of developing both at home and abroad in the last few years, has the shock strength height, characteristics such as surface property is good are fit to thin-walled injection molding, and product is mainly used in fiber, coating, washing machine inner tub and component, appliance shell etc.At present, the PP that China produces mostly is general purpose grade, and the mobile PP market has openings at home of the height of injection grade is very big, the dependence on import that need more than half approximately.At present, the preparation method of High Flowability PP mainly contains polymerization and regulates two kinds of method and granulation edman degradation Edmans.
(1) method is regulated in polymerization.The advantage of this method is less demanding to chosen process, produces steadily, and shortcoming is that the transition material is many, and polyreaction control difficulty is bigger.
(2) granulation edman degradation Edman.Promptly add degradation agents in the PP granulation process, (MFI) is adjusted to 20-50g/10min with its melt flow index.The advantage of this method is that switching process is short, and the transition material is less, product molecular weight distribution narrow (being generally 2-3), and excellent performance, and polyreaction control is simple, does not need special adjustment.But the uniformity coefficient that degradation agents adds is difficult to guarantee that therefore can cause resin palliating degradation degree difference, bias of index number is bigger, and flowing property is under some influence, and resin melt viscosity is little, makes that the granulation difficulty is big, and is wayward.
The ultimate principle of above-mentioned two kinds of production methods all is that a part of macromolecular chain in the PP resin is shortened, and reduces molecular-weight average and molecular weight distribution is broadened, and therefore is that sacrificing mechanical property is the fluidity of molten that cost improves PP with the reduction molecular weight in essence.
The patented invention of Chinese patent publication number 1405200 a kind of superbrnaching end-hydroxy polyester and preparation method thereof, resulting polymers contains a large amount of terminal hydroxy group, degradable, suitable efficient coating, tensio-active agent, biological medicine carrier, linking agent, rheology processing additives, the functional materials precursor etc. done.Y.Hong; S.J.Coombs; J.J.Cooper-White; M.E.Mackay; C.J.Hawker; E.Malmstr m; N.Rehnberg Polymer, 2000,41, the 7705-7713 processing aid of hyperbranched polymer as linear low density of polyethylene, the melt viscosity of finding blend descends, accelerate in certain extruded velocity current downflow, thereby extrude required energy and obviously reduce, eliminated the surface imperfection that often occurred in the former course of processing simultaneously.US Pat.6673870 adopts hyperbranched polymer to improve polyolefinic tensile property.
The present invention is intended to hyperbranched polymer under the situation that does not change acrylic resin molecular weight and distribution thereof, can improve polyacrylic fluidity of molten as polyacrylic rheology modifier greatly.
Summary of the invention
The object of the present invention is to provide a kind of raising fluidity of molten polypropylene, reduce the machine-shaping method of temperature.
The objective of the invention is to implement like this: with terephthalate, polyvalent alcohol is starting raw material, adding organic solvent dissolves it, react at a certain temperature after adding appropriate amount of catalysts then, after question response is complete product is precipitated out in deionized water and dries, obtain hyperbranched polymer.Then with this hyperbranched polymer with certain proportion with carry out injection moulding after polypropylene (PP) mixes.
Method of the present invention can be divided into for three steps:
The preparation of the first step hyperbranched polymer; The preparation of the PP master batch of the second step high-content hyperbranched polymer; The 3rd step was contained the PP injection moulding processing of hyperbranched polymer.
Now details are as follows respectively:
1) preparation hyperbranched polymer.
In organic solvent and under 140-220 ℃, polyvalent alcohol, terephthalate and catalyst reaction 5-100 hour, steam alcohol in the time of reaction; The mol ratio of described polyvalent alcohol and terephthalate is 1: 0.9～1: 3.2; The weight ratio of described terephthalate and catalyzer is 1: 0.00001～1: 0.0005; Described polyvalent alcohol is ternary or tetravalent alcohol.
Be starting raw material furtherly with the terephthalate.Earlier polyvalent alcohol is joined in the three-necked flask, polyvalent alcohol can be a TriMethylolPropane(TMP), tetramethylolmethane or 2-methylol 1, ammediol etc., algebraically (3-4 replacement) according to the synthetic hyperbranched polymer adds terephthalate then, as: dimethyl terephthalate (DMT) or diethyl terephthalate etc., and adding N, dinethylformamide (DMF) solvent dissolves above-mentioned raw materials, the zinc that adds 10-500ppm then, manganese, cobalt, acetic acid such as magnesium or calcium salt is as catalyzer (amount with terephthalate is that benchmark calculates), the best is 100-400ppm, temperature of reaction is risen to 140-220 ℃, preferably be controlled between 165-190 ℃, reacted 5-100 hour, Best Times is 20-60 hour.Begin to have alcohols to steam after being reflected at half an hour, finish, product is precipitated out oven dry in deionized water when no alcohols steams afterreaction.The mol ratio of tetravalent alcohol and terephthalic acid junket is 5: 16-17: 16, and the mol ratio of trivalent alcohol and terephthalate is 4: 9-10: 9.
2) preparation of the PP master batch of high-content hyperbranched polymer.
With the hyperbranched polymer of above-mentioned preparation with the weight ratio of 0.1-20% with after PP mixes, the best is 1-5%, 150-280 ℃ of process twin screw extruder blend granulation down, preparation has the PP master batch of high-content hyperbranched polymer, time through twin screw extruder is 1-10 minute, and the best is 3-7 minute.Perhaps
3) the PP injection moulding that contains hyperbranched polymer is processed.
With the PP master batch with high-content hyperbranched polymer of above-mentioned preparation according to the weight ratio of 1-100% with carry out injection moulding processing after PP mixes, injection moulding processing temperature scope is at 160-250 ℃, the best is 180-220 ℃, be 0-5 second inject time, the best is 1-3 second, can obviously reduce the temperature of injection moulding.
The present invention is that the reaction formula of example is as follows with tetravalent alcohol and dimethyl terephthalate (DMT):
Method of the present invention can under the situation that does not change acrylic resin molecular weight and distribution thereof, can improve polyacrylic fluidity of molten greatly with hyperbranched polymer as polyacrylic rheology modifier.Have that technology is simple, capable of reducing energy consumption, characteristics such as reduce production costs.
Description of drawings
Fig. 1 is the stereoscan photograph of hyperbranched polymer,
The infrared spectrogram of Fig. 2 hyperbranched polymer.
Embodiment
Take by weighing 93.2064 gram dimethyl terephthalate (DMT) (DMT) and be dissolved in N, the dinethylformamide (DMF) with 20.4225 gram tetramethylolmethanes, add catalyst acetic acid zinc 0.0202 gram, 180 ℃ of temperature of reaction were reacted 15 hours.Begin to have methyl alcohol to steam after being reflected at half an hour, finish, product is precipitated out oven dry in deionized water when no methyl alcohol steams afterreaction.Fig. 1 is mixed with dilute solution with reaction product and with after the solvent evaporates, observed situation under scanning electron microscope.Fig. 2 is the infrared spectrogram of hyperbranched polymer, has presented the feature of typical fragrant adoption junket.
Embodiment 2
Prepare the hyperbranched polymer that end group is a methoxyl group by example 1 described method, carry out the blend granulation with PP in twin screw extruder in certain proportion then, the melt flow index that adopts fusion index instrument to measure is as shown in table 1:
Table 1 adds the melt flow index of hyperbranched polymer front and back PP
| Hyperbranched polymer content (%) | Melt flow index MFI (g/10min/220 ℃) |
| 0 | 20.15 |
| 0.1 | 24.81 |
| 0.5 | 26.45 |
| 1.0 | 30.64 |
Prepare the hyperbranched polymer that end group is a methoxyl group by example 1 described method, with its with 1% ratio and PP through twin screw extruder blend granulation after, master batch mixed with PP carries out injection moulding and process, it is as shown in table 2 that injection moulding machine is respectively distinguished temperature:
The temperature in each district of table 2 injection moulding machine
| Hyperbranched polymer content (%) | Injection moulding machine respectively distinguish temperature (℃) | |||
| I | II | III | IV | |
| 0 | 205 | 195 | 190 | 175 |
| 0.05 | 200 | 190 | 185 | 175 |
| 0.10 | 195 | 185 | 180 | 175 |
| 0.15 | 185 | 175 | 170 | 165 |
| 0.20 | 185 | 175 | 170 | 165 |
Embodiment 4
Prepare the hyperbranched polymer that end group is a methoxyl group by example 1 described method, with its with 1% ratio and PP through twin screw extruder blend granulation after, again with master batch with carry out injection moulding after PP mixes and be processed into test bars after, the Mechanics Performance Testing result is as shown in table 4:
The mechanical property of table 4 PP/ hyperbranched polymer injection moulding batten
| Hyperbranched polymer content (%) | Tensile strength (MPa) | Yield strength (MPa) | Shock strength (KJ/m 2) | Young's modulus (Mpa) |
| 0 | 18.81 | 34.00 | 54.70 | 188.34 |
| 0.05 | 17.94 | 32.57 | 55.27 | 180.49 |
| 0.10 | 18.32 | 35.39 | 50.68 | 182.38 |
| 0.15 | 17.19 | 36.34 | 52.38 | 187.97 |
| 0.20 | 16.59 | 35.70 | 55.31 | 197.47 |
Claims (8)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103374118A (en) * | 2012-04-16 | 2013-10-30 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method and application of hyperbranched polyester |
| CN102926017A (en) * | 2012-11-09 | 2013-02-13 | 东华大学 | Hyperbranched polymer modifying dyeing fine denier polypropylene fiber and preparation method thereof |
| CN103192537A (en) * | 2013-04-27 | 2013-07-10 | 北京化工大学 | Method for injection moulding of hyperbranched polymer-monopolymer composite material product |
| CN104804197A (en) * | 2015-04-16 | 2015-07-29 | 科达斯特恩(常州)汽车塑件系统有限公司 | Halogen-free hyperbranched polymer and modified polypropylene containing same |
| CN106995550A (en) * | 2016-01-26 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of ultrabranching polyamide modified polypropylene composite material and preparation method thereof |
| CN109651700A (en) * | 2018-11-28 | 2019-04-19 | 江苏松上科技有限公司 | A kind of permanent conductive plastics particle and preparation method thereof |
| CN112853527B (en) * | 2021-01-07 | 2023-06-13 | 广东金发科技有限公司 | Melt-blown polypropylene composite material and preparation method and application thereof |
| CN113372613B (en) * | 2021-06-21 | 2022-07-12 | 万华化学(四川)有限公司 | Composite modifier for reducing melt index of polypropylene, preparation method and application thereof, and granulation process of high melt index polypropylene |
| CN114409999B (en) * | 2021-12-31 | 2024-12-06 | 金发科技股份有限公司 | A polypropylene composition and preparation method thereof |
| CN114836901B (en) * | 2022-05-30 | 2023-01-31 | 江阴市宏勇医疗科技发展有限公司 | Production method of activated carbon melt-blown non-woven fabric used as medical and health material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405200A (en) * | 2002-11-07 | 2003-03-26 | 上海交通大学 | Terminal hydroxy superbranched polyester |
| WO2003097740A1 (en) * | 2002-05-13 | 2003-11-27 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003097740A1 (en) * | 2002-05-13 | 2003-11-27 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
| CN1405200A (en) * | 2002-11-07 | 2003-03-26 | 上海交通大学 | Terminal hydroxy superbranched polyester |
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