CN100368472C - Method for improving fluidity of molten polypropylene - Google Patents
Method for improving fluidity of molten polypropylene Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- hyperbranched polymer
- terephthalate
- alcohol
- improves fluidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 polypropylene Polymers 0.000 title claims abstract description 39
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000001746 injection moulding Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 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
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract 2
- 238000006555 catalytic reaction 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
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 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
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000006254 rheological additive Substances 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
Images
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a method for improving the melt fluidity of polypropylene, which comprises the following steps: 1) polyatomic alcohol and terephthalate under the catalysis of a catalyst react in an organic solvent at the temperature of 140 to 220DEG C to obtain a hyperbranched polymer; 2) the prepared hyperbranched polymer and polypropylene are blended in a cross mode and granulated through a double-screw extruding machine at the temperature of 150 to 280DEG C to obtain polypropylene parent granules having a high content of the hyperbranched polymer; 3) alternatively, after being mixed, the prepared polypropylene parent granules having a high content of the hyperbranched polymer and polypropylene are processed in an injection forming mode according to the proportion of 1 to 100% by weight to obtain the polypropylene containing the hyperbranched polymer. The polypropylene containing the hyperbranched polymer can be obtained by using the hyperbranched polymer as a rheologic modifying agent for the polypropylene with the method of the present invention. The melt fluidity of the polypropylene can be greatly improved under the condition without changing the molecular weight and the molecular weight distribution of polypropylene resin. The present invention has the characteristics of simple process, energy consumption reduction, production cost reduction, etc.
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)
1. method that improves fluidity of molten polypropylene is characterized in that adopting following steps:
1) preparation of hyperbranched polymer,
In organic solvent and under 140-220 ℃, polyvalent alcohol, terephthalate were reacted 5-100 hour under catalyst, steamed 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; Product is precipitated out oven dry in deionized water;
2) preparation of the polypropylene agglomerate of high-content hyperbranched polymer,
With the hyperbranched polymer of above-mentioned preparation and the polypropylene agglomerate of polypropylene process twin screw extruder blend granulation acquisition high-content hyperbranched polymer under 150-280 ℃; The weight ratio of described polypropylene and hyperbranched polymer is 1: 0.001～1: 0.20; Or
3) the polypropylene injection moulding that contains hyperbranched polymer is processed,
With the polypropylene agglomerate with high-content hyperbranched polymer of above-mentioned preparation according to the weight ratio of 1-100% with carry out injection moulding processing after polypropylene mixes, injection moulding processing temperature scope is at 160-250 ℃, be 0-5 second inject time.
2. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 1) in, temperature of reaction is 165-190 ℃, the reaction times is 20-60 hour.
3. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 1) in, when described polyvalent alcohol was tetravalent alcohol, the mol ratio of tetravalent alcohol and terephthalate was 5: 16-17: 16; When described polyvalent alcohol was trivalent alcohol, the mol ratio of trivalent alcohol and terephthalate was 4: 9-10: 9.
4. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 1) in, described solvent is N, dinethylformamide.
5. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 1) in, the weight ratio of described terephthalate and catalyzer is 1: 0.0001-1: 0.0004.
6. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 2) described in polypropylene and the weight ratio of hyperbranched polymer be 1: 0.01～1: 0.05.
7. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 2) described in time of twin screw extruder be 1-10 minute.
8. a kind of according to claim 1 method that improves fluidity of molten polypropylene is characterized in that described method 3) described in the injection moulding processing temperature be 180-220 ℃, be 1-3 second inject time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100306179A CN100368472C (en) | 2005-10-18 | 2005-10-18 | Method for improving fluidity of molten polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100306179A CN100368472C (en) | 2005-10-18 | 2005-10-18 | Method for improving fluidity of molten polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1760252A CN1760252A (en) | 2006-04-19 |
| CN100368472C true CN100368472C (en) | 2008-02-13 |
Family
ID=36706490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100306179A Expired - Fee Related CN100368472C (en) | 2005-10-18 | 2005-10-18 | Method for improving fluidity of molten polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100368472C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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***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 |
| CN114409999A (en) * | 2021-12-31 | 2022-04-29 | 金发科技股份有限公司 | 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 |
-
2005
- 2005-10-18 CN CNB2005100306179A patent/CN100368472C/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1760252A (en) | 2006-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100368472C (en) | Method for improving fluidity of molten polypropylene | |
| CN102268144B (en) | Biodegradable polylactic acid-starch thermal-resistance composite material and preparation method thereof | |
| CN101891923B (en) | Method for preparing low-temperature flexible random copolymerization polypropylene product | |
| CN102529056B (en) | Preparation method for high melt strength poly lactic acid, and extruder thereof | |
| CN101747600B (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| KR20120037978A (en) | Thermoplastic resin composition and molded article of same | |
| CN102492101B (en) | ABS melt-grafting glycidyl methacrylate and preparation method thereof | |
| CN104530664A (en) | Modified-PET (polyethylene terephthalate)-based board, and processing method and device thereof | |
| CN102492225A (en) | Transparent cold resistance high melt-strength polypropylene material used for automobile expansion water tank and its preparation method | |
| CN108948690A (en) | A kind of polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN106674923A (en) | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film and preparation method thereof | |
| CN112920567A (en) | Wheat straw filled modified PLA fully-degradable plastic and preparation method thereof | |
| CN103589064B (en) | One relatively wide molecular weight distribution HOPP process for preparing resins | |
| CN102382265B (en) | Polybasic grafted polyethylene and preparation method thereof | |
| CN105531320B (en) | Include the resin combination of polymerized thylene carbonate hydrocarbon ester | |
| CN106751568A (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN113563696B (en) | Preparation method of modified polyethylene terephthalate | |
| CN114685961B (en) | Modified polylactic acid film material | |
| CN112321999B (en) | Preparation method of hyperbranched polybutylene adipate terephthalate material | |
| CN105086393A (en) | Plastic allowing PLA to be fully degraded and production method thereof | |
| CN113308100B (en) | Biodegradable polylactic acid/lignin composite material, preparation method and application | |
| CN109438602A (en) | A kind of polypropylene dedicated resin of high fondant-strength plastics sucking moulding and preparation method | |
| CN114106538A (en) | Fully-degradable plastic processing technology | |
| CN114605821A (en) | Bio-based nylon material and preparation method thereof | |
| CN110903486B (en) | Compatilizer, preparation method thereof and PET/inorganic filler composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: ZHEJIANG KINLEAD PACKAGING MATERIAL Co.,Ltd. Assignor: Donghua University Contract fulfillment period: 2009.4.27 to 2025.10.17 Contract record no.: 2009330000883 Denomination of invention: Method for improving fluidity of molten polypropylene Granted publication date: 20080213 License type: Exclusive license Record date: 20090507 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.27 TO 2025.10.17; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROV KAILI PACKAGING MATERIALS CO., LTD. Effective date: 20090507 |
|
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG PROV KAILI PACKAGING MATERIALS CO., LTD. Free format text: FORMER OWNER: DONGHUA UNIV. Effective date: 20100129 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20100129 Address after: No. 889, mirror Road, Keqiao East Industrial Park, Shaoxing County, Zhejiang Patentee after: ZHEJIANG KINLEAD PACKAGING MATERIAL Co.,Ltd. Address before: No. 1882, West Yan'an Road, Shanghai, Changning District Patentee before: Donghua University |
|
| C56 | Change in the name or address of the patentee |
Owner name: ZHEJIANG KINLEAD INNOVATIVE MATERIALS CO., LTD. Free format text: FORMER NAME: ZHEJIANG KINLEAD PACKAGING MATERIAL CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 312030 Zhejiang County of Shaoxing province Keqiao Street East Ke High-tech Park No. 889 water mirror Patentee after: ZHEJIANG KINLEAD INNOVATIVE MATERIALS Co.,Ltd. Address before: 312030 No. 889, mirror Road, Keqiao East Industrial Park, Shaoxing County, Zhejiang Patentee before: ZHEJIANG KINLEAD PACKAGING MATERIAL Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080213 Termination date: 20211018 |