CN102101903B - Method for preparing organosilane crosslinked polyethylene with long quality guarantee period by solid one-step process - Google Patents
Method for preparing organosilane crosslinked polyethylene with long quality guarantee period by solid one-step process Download PDFInfo
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Abstract
The invention discloses a method for preparing organosilane crosslinked polyethylene with a long quality guarantee period by a solid one-step process, which comprises the following steps: (1) kneading a silanol composite catalyst, a metal passivator, an antioxygen, a processing aid and a polyolefin polymer, extruding and granulating the mixture, immersing the obtained catalyst master batch grains in molten protective agent, collecting the catalyst master batch grains and drying; and (2), mixing the product obtained by the step (1) with polyvinyl resin, polypropylene, silane crosslinking agent, peroxide crosslinking agent and antioxygen at normal temperature to obtain the solid one-step process organosilane crosslinked polyethylene with a long quality guarantee period. The method can prevent the condensation reaction of the silane crosslinking agent and the catalyst. The quality guarantee period of the solid one-step process organosilane crosslinked polyethylene is more than one year. The solid one-step process organosilane crosslinked polyethylene has high processability and degree of cross linking and is suitable to be processed under normal conditions.
Description
Technical field
The present invention relates to a kind of solid phase single stage method and produce the method for organosilane crosslinked polyethylene.
Technical background
Organosilane crosslinked polyethylene adopts the silicomethane method usually, is a kind of known single stage method.Therefore this method need exist problems such as error in dipping with the liquid feeding equipment of organic undersaturated silane with the form injection forcing machine of liquid.And this method needs the expensive forcing machine of the specific type of high length-diameter ratio, and equipment interoperability is poor.In addition, in extruding, also need very high technology.
Known single stage method is that disclosed silane is added to the silane cross-linking method in the solid carrier polymkeric substance among JP-A-3-167229, CN1198177A, the CN01105229.5 in addition.The oligomeric cross-linking efficiency that causes that this method exists silane condensation to produce low with problem such as poor storage stability.
Like disclosed in CN01105229.5 " solid-state one-step method silanes crosslinked polyolefinic method "; Be after containing organic unsaturated silane and free-radical generating agent, silanol condensation catalyst and oxidation inhibitor etc. and mediating in the polynary composite micro-powder solid carrier that is substantially free of water, to be blended into silane cross-linked polyolefin with polyolefin polymer again.
This solid-state one-step silane cross-linked polyethylene method, employing be the very big dibutyl tin laurate silanol condensation catalyst of catalytic activity, and it is kneaded into catalyst masterbatch with organic unsaturated silane.Meeting such as silanol condensation catalyst dibutyl tin laurate reacts with silane crosslinker vinyl trimethylsilane/vinyl triethyl silicane in the process of producing and preserving, and causes the organosilane crosslinked polyethylene degree of crosslinking low, even can't be crosslinked.After generally depositing 2 months, because silane crosslinker and silanol condensation catalyst generation condensation reaction cause the single stage method crosslinked polyethylene to scrap.
Summary of the invention
The purpose of this invention is to provide the method that a kind of solid-state single stage method of growing the quality guaranteed period prepares organosilane crosslinked polyethylene, exist and understand above-mentioned defective to overcome prior art.
Method of the present invention comprises the steps:
(1) with silanol composite catalyst, metal passivator, oxidation inhibitor, processing aid and polyolefin polymer; Under 115～130 ℃ temperature, mediate extruding pelletization, obtain the catalyst masterbatch particle; Then the catalyst masterbatch impregnated with particles that obtains was stirred in the fused protective material 30～600 seconds; Regather the catalyst masterbatch particle, drying obtains the surface and has wrapped up protectant catalyst masterbatch particle;
It is 2000～10000 low molecular weight polyethylene that said protective material is selected from paraffin, molecular-weight average, preferred paraffin;
Component and parts by weight are that this area is commonly used, preferably:
0.05～1.5 part of silanol composite catalyst, 0.05～2.5 part of metal passivator, 0.02～2.5 part in oxidation inhibitor, 0～5 part of processing aid, 50～100 parts of polyolefin polymers.
Said silanol composite catalyst is the mixture of alkaline amine thing and carboxylic acid, and said alkaline amine thing is selected from 4-amino-α, α; 4-trimethylammonium-hexanaphthene alkanamine in the Meng, 1,4-diamino--hexanaphthene alkanamine in the Meng or 1,4-diamino--α; α, 4-second methyl-cyclohexyl alkane alkanamine in the Meng; Said carboxylic acid is preferably formic acid; The weight ratio of alkalescence amine thing and carboxylic acid is: alkaline amine thing: carboxylic acid=1: 0.8～1.5 are preferably: alkaline amine thing: carboxylic acid=1: 1;
Described metal passivator is a hydrazide compound; Preferably, said metal passivator is selected from salicylamide base phthalic imidine, two (3,5-di-t-butyl-4-phenylor propionyl group) hydrazine or N, more than one in N ' diphenylmethylene ethanedioyl two hydrazides;
Used oxidation inhibitor be selected from four (3-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (code name 1010), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol) (code name 300), N, N '-1; [3-(3 for 6-hexylidene-two; The 5-di-tert-butyl-hydroxy phenyl) propionic acid amide (code name 1098), 4,4 '-one or more of thiobis (phenol between the 6-tertiary butyl), three (2, the 4-tert-butyl phenol) phosphorous acid ester; Preferably, said oxidation inhibitor is more than one in 1010 or 300;
Said processing aid is selected from more than one in ethylene-propylene-diene monomer glue elastomer, polyolefin elastomer, low molecular weight polyethylene wax or the viton;
It is 0.910～0.940g/cm that said polyolefin polymer can be selected density for use
3, melting index is the multipolymer of alhpa olefin of Vilaterm or ethene and 4～12 carbon of 0.1～25g/10min; Preferably, said polyvinyl resin is the multipolymer of ethene and octene, amylene or hexene;
(2) product with step (1) mixes with polyvinyl resin, acrylic resin, silane crosslinker, peroxide cross-linking agent and oxidation inhibitor at normal temperatures, can obtain the solid-state one-step silane cross-linked polyethylene of long quality guaranteed period;
Component and parts by weight are that this area is commonly used, preferably:
70～100 parts of polyvinyl resins, 1～30 part of acrylic resin, 0.6～3 part of silane crosslinker, 0.01～3 part of peroxide cross-linking agent, 0.02～5 part in oxidation inhibitor; The weight consumption of the product of step (1) is 2～5% of a product gross weight.
The same step of the oxidation inhibitor of selecting for use (1);
Described silane crosslinker is an organosilicon; More than one in vinyl silane triisopropoxide, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three-(2-methoxy ethoxy) silane and the dimethyldiethoxysilane preferably; Preferably, said silane crosslinker is vinyltrimethoxy silane, vinyltriethoxysilane or its mixture.
The invention has the beneficial effects as follows: can prevent silane crosslinker and catalyzer generation condensation reaction; A kind of working method of growing the solid-state one-step silane cross-linked polyethylene of quality guaranteed period is provided; The solid-state one-step silane cross-linked polyethylene quality guaranteed period of the present invention reached more than 12 months; Have better processing characteristics and degree of crosslinking, be adapted at processing under the normal condition.
Embodiment
Among the embodiment, if no special instructions, be weight part.
Embodiment 1
With 1 part of 4-amino-α, α, 4-trimethylammonium-hexanaphthene alkanamine in the Meng, 1 part of formic acid, 3 parts of salicylamide base phthalic imidines, 0.5 part four (3-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 100 parts of polyvinyl resins in kneader 130 ℃ mediate down, extruding pelletization obtains the catalyst masterbatch particle; Then with the catalyst masterbatch impregnated with particles that obtains in fused paraffin; Stirred 100 seconds, and filtered the collection catalyst masterbatch pellet then; Drying obtains the catalyst masterbatch particle that paraffin has been wrapped up on the surface;
Then; With above-mentioned parcel the catalyst masterbatch particle of paraffin, 95 parts of polyvinyl resins, 5 parts of acrylic resins, 2 parts of vinyl silane triisopropoxides, 1 part of Di Cumyl Peroxide 99 and 0.5 part four (3-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixes at normal temperatures, can obtain product.
The described catalyst masterbatch particulate weight consumption that has wrapped up paraffin is 2% of a product gross weight.Detected result is seen table 1.
Embodiment 2
With 1 part 1,4-diamino--hexanaphthene alkanamine in the Meng, 1 part of formic acid, 3 parts of salicylamide base phthalic imidines, 0.5 part four (3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 100 parts of polyvinyl resins in kneader 115 ℃ mediate down; Extruding pelletization; Obtain the catalyst masterbatch particle, then with the catalyst masterbatch impregnated with particles that obtains in fused paraffin, stirred 100 seconds; Filter then; The collection catalyst masterbatch pellet, drying obtains the catalyst masterbatch particle that paraffin has been wrapped up on the surface;
Then with the above-mentioned catalyst masterbatch particle that has wrapped up paraffin and 100 parts of polyvinyl resins, 5 parts of acrylic resins, 2 parts of vinyl silane triisopropoxides, 1 part of Di Cumyl Peroxide 99 and 0.5 part four (3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixes at normal temperatures and gets final product.
The described catalyst masterbatch particulate weight consumption that has wrapped up paraffin is 2% of a product gross weight.Detected result is seen table 1.
Embodiment 3
This embodiment is to be enclosed with protective material employing low molecular weight polyethylene with the difference of embodiment 1.
With 1 part of 4-amino-α, α, 4-trimethylammonium-hexanaphthene alkanamine in the Meng, 1 part of formic acid, 3 parts of salicylamide base phthalic imidines, 0.5 part four (3-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 100 parts of polyvinyl resins in kneader 115 ℃ mediate down; Obtain the catalyst masterbatch particle, then with the catalyst masterbatch impregnated with particles that obtains in the fused molecular-weight average is 2000 low molecular weight polyethylene, stirred 30 seconds; Filter then; The collection catalyst masterbatch pellet, drying obtains the catalyst masterbatch particle that low molecular weight polyethylene has been wrapped up on the surface;
Then with above-mentioned wrapped up the catalyst of polyethylene masterbatch pellet with 100 parts of polyvinyl resins, 5 parts of acrylic resins, 2 parts of vinyl silane triisopropoxides, 1 part of Di Cumyl Peroxide 99 and 0.5 part four (3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixes at normal temperatures and gets final product.
The described weight consumption that has wrapped up the catalyst of polyethylene masterbatch pellet is 2% of a product gross weight.Detected result is seen table 1.
Embodiment 4
Adopt identical method with embodiment 3, difference is that the catalyst masterbatch consumption is 5%.Detected result is seen table 1.
Table 1
Tensile strength adopts the GB/T1040.3 standard, and elongation at break adopts the GB/T1040.3 standard, and maximum elongation rate % cooling back permanent production rate adopts the GB/T2951.21 standard under the heat extension load, and degree of crosslinking adopts the JB/T10437 standard.
Claims (4)
1. the solid-state single stage method of growing the quality guaranteed period prepares the method for organosilane crosslinked polyethylene, it is characterized in that, comprises the steps:
(1) will be as the alkaline amine thing of composite catalyst and mixture, metal passivator, oxidation inhibitor, processing aid and the polyolefin polymer of carboxylic acid; Mediate extruding pelletization; Then with the catalyst masterbatch impregnated with particles that obtains in the fused protective material; Regather the catalyst masterbatch particle, drying obtains the surface and has wrapped up protectant catalyst masterbatch particle;
It is 2000～5000 low molecular weight polyethylene that said protective material is selected from paraffin or molecular weight;
(2) product with step (1) mixes with polyvinyl resin, acrylic resin, silane crosslinker, peroxide cross-linking agent and oxidation inhibitor at normal temperatures, can obtain the solid-state one-step silane cross-linked polyethylene of long quality guaranteed period.
2. method according to claim 1 is characterized in that, in the step (1), component and parts by weight are:
0.05～1.5 part of said composite catalyst, 0.05～2.5 part of metal passivator, 0.02～2.5 part in oxidation inhibitor, 0～5 part of processing aid, 50～100 parts of polyolefin polymers.
3. method according to claim 1 is characterized in that, in the step (2); The parts by weight of component are: 70～100 parts of polyvinyl resins, 1～30 part of acrylic resin, 0.6～3 part of silane crosslinker; 0.01～3 part of peroxide cross-linking agent, 0.02～5 part in oxidation inhibitor; The weight consumption of the product of step (1) is 2～5% of a product gross weight.
4. method according to claim 1 is characterized in that, in the step (2), described silane crosslinker is an organosilicon.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464005A (en) * | 2002-06-11 | 2003-12-31 | 上海高分子功能材料研究所 | Silicon alkyl cross bonding polyethylene fire-retardancy insulating plastics |
| CN1482204A (en) * | 2002-09-11 | 2004-03-17 | 云南玮昊能源发展有限公司 | Energy-accumulating temp-controlled thermoplastic cross-link high-molecular composite material with solid-solid phase change and its preparing process |
| CN101134826A (en) * | 2006-08-29 | 2008-03-05 | 上海高分子功能材料研究所 | Foaming silane crosslinked polyethylene plastic and method for preparing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464005A (en) * | 2002-06-11 | 2003-12-31 | 上海高分子功能材料研究所 | Silicon alkyl cross bonding polyethylene fire-retardancy insulating plastics |
| CN1482204A (en) * | 2002-09-11 | 2004-03-17 | 云南玮昊能源发展有限公司 | Energy-accumulating temp-controlled thermoplastic cross-link high-molecular composite material with solid-solid phase change and its preparing process |
| CN101134826A (en) * | 2006-08-29 | 2008-03-05 | 上海高分子功能材料研究所 | Foaming silane crosslinked polyethylene plastic and method for preparing the same |
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