CN102585328B - Peroxide cross-linked polyolefin and preparation method thereof - Google Patents
Peroxide cross-linked polyolefin and preparation method thereof Download PDFInfo
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- CN102585328B CN102585328B CN201110461700.7A CN201110461700A CN102585328B CN 102585328 B CN102585328 B CN 102585328B CN 201110461700 A CN201110461700 A CN 201110461700A CN 102585328 B CN102585328 B CN 102585328B
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- 150000002978 peroxides Chemical class 0.000 title claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 23
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 11
- -1 sulphur ester Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005469 granulation Methods 0.000 abstract description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000003921 oil Substances 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 150000007970 thio esters Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000426 Microplastic Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000004717 peroxide crosslinked polyethylene Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a peroxide cross-linked polyolefin and a preparation method thereof. The peroxide cross-linked polyolefin comprises the following components based on the total weight: 96 to 98 percent of low density polyethylene, 1.5 to 3 percent of dicumyl peroxide, and 0.1 to 1.0 percent of LAT-300, wherein the LAT-300 is one or more of liquid silicon oil, thiophenol antioxidant, thioester antioxidant and hindered phenol antioxidant; and the LAT-300 is bound to contain the liquid silicon oil. The invention has the advantages that (1) energy is saved, the peroxide cross-linked polyolefin can be prepared through a drum or stirring equipment in the process according to the preparation method, re-melting and re-granulation are not required, the consumption of the energy is reduced, the production cost is further reduced, and the preparation method has great practical production significance; and (2) the performance of the polyolefin is excellent; and (3) the purity of the polyolefin is high.
Description
Technical field
Invention relates to a kind of polyolefine, and more specifically, particularly one can the polyolefinic preparation method of peroxide crosslinking.
Background technology
Peroxide crosslinking adopts peroxide cross-linking agent that polymkeric substance is produced to be cross-linked, and changes reticulated structure into by linear structure.Peroxide crosslinked polyethylene base-material, linking agent and oxidation inhibitor form.
Polyethylene is the polymkeric substance of monomer ethylene, peroxide crosslinked polyethylene base-material, usually adopts melt index to be the Low Density Polyethylene of about 2.0.Low Density Polyethylene is adopted to be that at the bottom of processing temperature, decomposition temperature can be used low, and cross-linking efficiency is high, the dicumyl peroxide that performance is good, can not cause incipient scorch because of the premature decomposition of superoxide in the course of processing because its degree of crystallinity is low.Certainly, along with the development of the peroxide cross-linking agent of high decomposition temperature, some performance may be made to be affected and to be easily out of shape in cross-linking process, and melt index is too low, then unfavorable to processing safety, and the slipperiness of compressive surface is affected.
Superoxide makes polyethylene produce crosslinked action linking agent, a good linking agent should meet following requirements: 1) decomposition temperature of superoxide had both been higher than the fusing point of itself, again higher than poly fusing point, first melt before decomposition like this, easily mix.Resolution characteristic curve is precipitous, i.e. little disintegration before not reaching decomposition temperature, and once reaches decomposition temperature and can decompose rapidly and completely.
2) superoxide work range is wide, good processability and cross-linking efficiency is high.
3) superoxide will have high concentration and purity, pollution-free, low volatility, and its resolvent will lack, and requires that resolvent easily volatilizees.
The organo-peroxide that can meet above-mentioned requirements is little, is best at present for the linking agent of crosslinked polyethylene with dicumyl peroxide.
The consumption of linking agent should affect angle to select on performance from it, and dosage of crosslinking agent is large, then machinery, thermotolerance, oil resistant and resistance to dissolubility enhancing, is then deteriorated to electrical property, shock resistance and winter hardiness.
Oxidation inhibitor, in order to prevent the deterioration by oxidation of crosslinked polyethylene in processing and use procedure, must add oxidation inhibitor.Oxidation inhibitor has the decomposition stoping superoxide and the radical absorbing peroxide breakdown, and make it that chain not occur and destroy reaction, these effects also can be reflected on the superoxide as linking agent, make linking agent not easily produce crosslinking reaction.Because requiring existing high antioxidant effect at selected oxidation inhibitor, can be minimum to the disadvantageous effect of crosslinking reaction again, and nontoxic.Current most domestic manufacturer have employed 300# oxidation inhibitor, but its fusing point is high, not easily mixes, therefore some manufacturer adopts fusing point to be that 90 DEG C of oxidation inhibitor are with the 300# oxidation inhibitor replacing 165 DEG C, but because aging resistance and processing characteristics fail to reach a standard, be not thus promoted.
Former operational path enters Fig. 1, and its defect is 1) polyvinyl resin needs granulation again, and resin characteristics and electrical property are had a significant impact, too increases resin by the chance again polluted simultaneously.
2) linking agent easily decomposes in this process in advance, and acts on polyvinyl resin, causes polythene working property greatly to decline.
3) oxidation inhibitor existing more ripe application mostly at present is antioxidant 300 #, but its fusing point is higher, differs comparatively large, the therefore more difficult grasp of its dispersity with the Low Density Polyethylene fusing point of existing use.
Summary of the invention
The object of the invention is to the deficiency overcoming above-mentioned existence, provide one can peroxide crosslinking polyolefine and preparation method thereof.
A kind of peroxide crosslinking polyolefine, described peroxide crosslinking polyolefine comprises following compositions by total weight:
96% ~ 98% Low Density Polyethylene (LDPE);
The dicumyl peroxide (DCP) of 1.5% ~ 3%;
The LAT-300 of 0.1% ~ 1.0%, described LAT-300 are one or more compositions of liquid silicone oil, thiophenols oxidation inhibitor, sulphur ester antioxidant, Hinered phenols antioxidant, and wherein said LAT-300 must contain liquid silicone oil.
Preferably, described LAT-300 is liquid silicone oil.
A kind of peroxide crosslinking polyolefine, described peroxide crosslinking polyolefine comprises following compositions by total weight:
96% ~ 98% Low Density Polyethylene (LDPE);
The dicumyl peroxide (DCP) of 1.5 ~ 3%;
The PAT-300 of 0.1% ~ 1.0%, described PAT-300 are thiophenols oxidation inhibitor, sulphur ester antioxidant, Hinered phenols antioxidant, suffocated amine antioxidant, one or more compositions of stearate, and wherein said PAT-300 must contain stearate.
Preferably, described PAT-300 is stearate.
Another embodiment of the present invention, a kind of peroxide crosslinking process for preparing polyolefins, its preparation method comprises the steps:
5) DCP, LAT-300 or PAT-300 are carried out premix according to ratio in material storage kettle for subsequent use, temperature is set to 75-100 DEG C;
6) by rotary drum or whipping device preheating 75-95 DEG C, after reaching preheating temperature, quantitative Low Density Polyethylene is added, preheating more than 20 minutes, open vacuum unit, negative pressure more than setting-0.01Mpa, vacuum-treat is more than 20 minutes, and in this process, whipping device need carry out low cruise;
7) after vacuum-treat is complete, quantitatively add DCP, LAT-300 or PAT-300 mixed solution mixed in advance, now sprue place can filter;
8) rotary drum or whipping device are remained in operation, infiltrate absorption more than 1h, can shut down equipment discharging, and this process intermittently can complete or can complete continuously.
The positive progressive effect that the present invention obtains is:
(1) energy-conservation, preparation method of the present invention just can realize by means of only rotary drum or whipping device during the course can the polyolefinic preparation of peroxide crosslinking, does not need again melt pelletization to process, has saved energy consumption, and then reduce production cost, larger to actual production meaning.
(2) excellent product performance, because polyolefine does not experience melt blending, thermal history is relatively short, therefore high degree remain basic physical properties.
(3) product high purity, for preparing through the method can maintain the initial purity of plastic pellet by peroxide crosslinking polyolefine substantially, and secondary pollution is very little, therefore for the research and development preparation of the preparation product of resistance to ultra-high voltage provides technological accumulation.
Accompanying drawing explanation
Fig. 1 is the process route chart of prior art;
Fig. 2 be the present invention process route chart.
Embodiment
Embodiment 1
Present invention process: one can peroxide crosslinking polyolefin component be:
The LDPE of 97.0 weight fractions;
The DCP of 2.5 weight fractions;
The liquid silicone oil of 0.3 weight fraction or stearate.
One can the polyolefinic preparation method of peroxide crosslinking, and its preparation method comprises the steps:
1) by DCP, it is for subsequent use that liquid silicone oil or stearate carry out premix according to ratio in material storage kettle, and temperature is set to 75-100 DEG C;
2) by rotary drum or whipping device preheating 75-95 DEG C, after reaching preheating temperature, quantitative LDPE is added, preheating more than 20 minutes, open vacuum unit, negative pressure more than setting-0.01Mpa, vacuum-treat is more than 20 minutes, and in this process, whipping device need carry out low cruise;
3) after vacuum-treat is complete, quantitatively add DCP, LAT-300 or PAT-300 mixed solution mixed in advance, now sprue place can filter;
4) rotary drum or whipping device are remained in operation, infiltrate absorption more than 1h, can shut down equipment discharging, and this process intermittently can complete or can complete continuously.
Former technique: one can peroxide crosslinking polyolefin component be:
97.3 weight fractions LDPE;
The DCP of 2.5 weight fractions;
The 300# of 0.2 weight fraction.
One can the polyolefinic preparation method of peroxide crosslinking, and its preparation method comprises the steps:
1) DCP, 300# are carried out premix according to ratio in material storage kettle for subsequent use, temperature is set to 75-100 DEG C;
2) by rotary drum or whipping device preheating 75-95 DEG C, after reaching preheating temperature, quantitative LDPE is added, preheating more than 20 minutes, open vacuum unit, negative pressure more than setting-0.01Mpa, vacuum-treat is more than 20 minutes, and in this process, whipping device need carry out low cruise;
3) after vacuum-treat is complete, quantitatively add DCP, 300# mixed solution mixed in advance, now sprue place can filter;
4) rotary drum or whipping device are remained in operation, infiltrate absorption more than 1h, can shut down equipment discharging, and this process intermittently can complete or can complete continuously.
The comparative data of the present invention and former technique is as follows:
One, rheological behaviour
Two, heat extends
Three, impurity
Four, heterogel body
Five, outward appearance
| Outward appearance | |
| The present invention | Pure white translucent, without obvious chip |
| Former technique | Color and luster is uneven, micro-Huang, and surperficial adularescent powder, has more chip |
So, the present invention can more energy-conservation than prior art of peroxide crosslinking polyolefine, preparation method of the present invention just can realize by means of only rotary drum or whipping device during the course can the polyolefinic preparation of peroxide crosslinking, melt pelletization is not needed again to process, save energy consumption, and then reduce production cost, larger to actual production meaning.
And preparation excellent product performance, because polyolefine does not experience melt blending, thermal history is relatively short, thus high degree remain basic physical properties.
The product high purity obtained, for preparing through the method can maintain the initial purity of plastic pellet by peroxide crosslinking polyolefine substantially, and secondary pollution is very little, therefore for the research and development preparation of the preparation product of resistance to ultra-high voltage provides technological accumulation.
Embodiment 2
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 96.0 weight fractions;
The DCP of 3.0 weight fractions;
The liquid silicone oil of 1.0 weight fractions and thiophenols oxidation inhibitor.
Embodiment 3
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 96.0 weight fractions;
The DCP of 3.0 weight fractions;
The liquid silicone oil of 1.0 weight fractions and Hinered phenols antioxidant.
Embodiment 4
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 96.0 weight fractions;
The DCP of 3.0 weight fractions;
The liquid silicone oil of 1.0 weight fractions and sulphur ester antioxidant.
Embodiment 5
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 98.0 weight fractions;
The DCP of 1.5 weight fractions;
The liquid silicone oil of 0.5 weight fraction and sulphur ester antioxidant.
Embodiment 6
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 98.0 weight fractions;
The DCP of 1.5 weight fractions;
The stearate of 0.5 weight fraction and thiophenols oxidation inhibitor.
Embodiment 7
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 98.0 weight fractions;
The DCP of 1.5 weight fractions;
The stearate of 0.5 weight fraction and suffocated amine antioxidant.
Embodiment 8
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 98.0 weight fractions;
The DCP of 1.5 weight fractions;
The stearate of 0.5 weight fraction and Hinered phenols antioxidant.
Embodiment 9
Instant component: one can peroxide crosslinking polyolefin component be:
The LDPE of 96.0 weight fractions;
The DCP of 3.0 weight fractions;
The stearate of 1.0 weight fractions and Hinered phenols antioxidant.
So far invention has been described in conjunction with the embodiments.Those skilled in the art should be appreciated that without departing from the scope and spirit of the present invention, easily can make other amendment various to described embodiment.Therefore, the scope of appended claims is not limited to above-mentioned explanation, but broadly will explain claim.
Claims (1)
1. the polyolefinic preparation method of peroxide crosslinking, is characterized in that: its preparation method comprises the steps:
1) by dicumyl peroxide, it is for subsequent use that LAT-300 or PAT-300 carries out premix according to part by weight in material storage kettle, and temperature is set to 75-100 DEG C;
2) by whipping device preheating 75-95 DEG C, after reaching preheating temperature, quantitative Low Density Polyethylene is added, preheating more than 20 minutes, open vacuum unit, negative pressure more than setting-0.01MPa, vacuum-treat is more than 20 minutes, and in this process, whipping device need carry out low cruise;
3) after vacuum-treat is complete, quantitatively add dicumyl peroxide mixed in advance, LAT-300 or PAT-300 mixed solution, now sprue place filters;
4) remained in operation by whipping device, infiltrate absorption more than 1h, can shut down equipment discharging, and this process intermittently can complete or can complete continuously;
Described LAT-300 is one or more compositions of liquid silicone oil, thiophenols oxidation inhibitor, sulphur ester antioxidant, Hinered phenols antioxidant, and wherein said LAT-300 must contain liquid silicone oil;
Described PAT-300 is thiophenols oxidation inhibitor, sulphur ester antioxidant, Hinered phenols antioxidant, suffocated amine antioxidant, one or more compositions of stearate, and wherein said PAT-300 must contain stearate;
Described peroxide crosslinking polyolefine comprises by total weight: 96% ~ 98% Low Density Polyethylene; The dicumyl peroxide of 1.5% ~ 3%; LAT-300 or PAT-300 of 0.1% ~ 1.0%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110461700.7A CN102585328B (en) | 2011-12-30 | 2011-12-30 | Peroxide cross-linked polyolefin and preparation method thereof |
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| CN201110461700.7A CN102585328B (en) | 2011-12-30 | 2011-12-30 | Peroxide cross-linked polyolefin and preparation method thereof |
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| CN102585328A CN102585328A (en) | 2012-07-18 |
| CN102585328B true CN102585328B (en) | 2015-03-25 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1343738A (en) * | 2000-09-20 | 2002-04-10 | 中国石油化工股份有限公司 | Chemically cross-linked millipore polyethene material and its preparing process |
| CN101230165A (en) * | 2008-02-28 | 2008-07-30 | 上海交通大学 | Preparation method of polyethylene-based thermoplastic wood-plastic composite material |
| CN101962453A (en) * | 2009-07-22 | 2011-02-02 | 中国石油天然气股份有限公司 | Polyethylene greenhouse film resin composition and preparation method thereof |
| CN102140193A (en) * | 2009-10-30 | 2011-08-03 | 中国石油化工股份有限公司 | Chemically cross-linked polyethylene composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1343738A (en) * | 2000-09-20 | 2002-04-10 | 中国石油化工股份有限公司 | Chemically cross-linked millipore polyethene material and its preparing process |
| CN101230165A (en) * | 2008-02-28 | 2008-07-30 | 上海交通大学 | Preparation method of polyethylene-based thermoplastic wood-plastic composite material |
| CN101962453A (en) * | 2009-07-22 | 2011-02-02 | 中国石油天然气股份有限公司 | Polyethylene greenhouse film resin composition and preparation method thereof |
| CN102140193A (en) * | 2009-10-30 | 2011-08-03 | 中国石油化工股份有限公司 | Chemically cross-linked polyethylene composition and preparation method thereof |
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