CN100457798C - Process for preparing silane crosslinked polyethylene by room temperature crosslinking - Google Patents
Process for preparing silane crosslinked polyethylene by room temperature crosslinking Download PDFInfo
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Abstract
The present invention is room temperature cross-linking process of preparing silane cross-linked polyethylene, and the silane cross-linked polyethylene is prepared with grafting material and catalytic material in the weight ratio of 5-20 to 1 and through room temperature cross-linking. The grafting material consists of polyethylene resin 100 weight portions, alkenyl alkoxy silane 0.5-5 weight portions, alkyl trimethoxy silane 0.5-3 weight portions, titanium-alkoxide chelate 0.5-3 weight portions and free radical initiator 0.01-2 weight portions. The catalytic material consists of polyethylene resin 100 weight portions, water generating agent 0.5-30 weight portions, cross-linking catalyst 1-5 weight portions. Compared with available technology, the present invention has the features of advanced technological process, high product yield, low power consumption, excellent product performance, etc.
Description
(1) technical field
The present invention relates to a kind of method of preparing silane crosslinked polyethylene by room temperature crosslinking, especially a kind of method of adding the preparing silane crosslinked polyethylene by room temperature crosslinking that produces aqua.
(2) background technology
Bigger application of organosilane crosslinked polyethylene is preparation CABLE MATERIALS and tubing, early stage organosilane crosslinked polyethylene, as introducing among the Chinese invention patent CN96119846.X, general stranding and Guan Houxu boil 6～12 hours through warm water or steam, or just can finish crosslinked in 15～20 days under field conditions (factors).This will greatly reduce production efficiency, consume a large amount of energy, and increase follow-up equipment and storehouse, cause costing an arm and a leg of organosilane crosslinked polyethylene, be difficult to apply on a large scale.Then have Chinese invention patent CN02151548.4 to introduce a kind of new organosilane crosslinked polyethylene, its composite a kind of stopper is to solve the too early crosslinked and long term storage stability problem of grafted material.In the recent period there is Chinese invention patent CN200310109010.0 to disclose the preparation method of room temperature organosilane crosslinked polyethylene again, improved the crosslinked condition of relative complex, make need originally just to finish under hot water or the steam condition crosslinked, at room temperature place and just can finish in 1～3 day.But last method mainly is suitable for HDPE, and not mentioned cross-linking method; Though the latter can be normal temperature crosslinked, crosslinked required water is to need to come in from extraneous scattering and permeating, certainly will be relevant with product thickness with envrionment conditions, thus make complicated operation, condition be difficult to control and then influence product performance.
(3) summary of the invention
The present invention be for provide a kind of add produce aqua, need not extraneously supply water when crosslinked, the method for easy and simple to handle, preparing silane crosslinked polyethylene by room temperature crosslinking that product performance are good.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of method of preparing silane crosslinked polyethylene by room temperature crosslinking, described method is with grafted material: alkenyl alkoxy silane grafted polyvinyl resin, with catalysing material: contain catalyzer, produce the polyvinyl resin of aqua, with 5～20: 1 mass ratio mixes, carry out crosslinkedly under the room temperature, promptly get described crosslinked polyethylene; The raw materials quality for preparing described grafted material and catalysing material is composed as follows:
Grafted material:
100 parts of polyvinyl resins
0.5～5 part of alkenyl alkoxy silane
0.5～3 part of alkyl trimethoxysilane
0.5～3 part of alkyl titanium oxide inner complex
0.01～2 part of radical initiator
Catalysing material:
100 parts of polyvinyl resins
Produce 0.5～30 part in aqua
1～5 part of crosslinking catalyst.
Described product aqua can be to contain the mixture that high temperature discharges inorganic salt, organic acid and the metal oxide of crystal water, or contain the polymkeric substance that high-temperature polycondensation can produce micromolecular water, specifically can be one of the following or mixture of two or more arbitrary proportion wherein: 1. with the sodium formiate of crystal water, 2. with the sodium-acetate of crystal water, 3. with the SODIUM PHOSPHATE, MONOBASIC of crystal water, 4. stearic acid and zinc oxide composites, 5. terpolycyantoamino-formaldehyde resin.Be preferably terpolycyantoamino-formaldehyde resin.Produce aqua can be in the polymer melt of lesser temps homodisperse and not discharging water, yet mix with certain proportion at grafted material, catalysing material, melt extrude through higher temperature, producing aqua then decomposes or react and produce micro-water and be present in material internal, make the crosslinked infiltration that need not rely on outside water of grafted silane hydrolyzate, and the required water of siloxanes hydrolytie polycondensation can be recycled, and do not need much so produce the consumption of aqua.Produce water that aqua generates except with siloxane reactions, main is the sol-gel transition that alkyl titanium oxide takes place, the in-situ nano particulate of its formation more has strengthening action to organosilane crosslinked polyethylene.Product at ambient temperature, in 48 hours summers, finish crosslinked 120 hours winters substantially, makes described organosilane crosslinked polyethylene.
Described polyvinyl resin is one of following or the mixture of two or more arbitrary proportion wherein: 1. low density polyethylene, 2. linear low density of polyethylene LLDPE, 3. high density polyethylene, 4. ethylene vinyl acetate EVA.Be preferably new LDPE (film grade) or linear low density of polyethylene.
Described alkenyl alkoxy silane is one of following or the mixture of two or more arbitrary proportion wherein: 1. vinyltriethoxysilane, 2. propenyl triethoxyl silane, 3. methacryloxypropyl triethoxyl silane.Be preferably vinyltriethoxysilane.
Described alkyl titanium oxide inner complex is four titanium butoxide and methyl ethyl diketone or 1: 1 inner complex of methyl aceto acetate mass ratio, or be four titanium butoxide respectively with the mixture of methyl ethyl diketone or ethyl acetoacetate chelate.Because the hydrolytie polycondensation speed of alkyl titanium oxide is much larger than silane oxide, meeting water in air is that hydrolytie polycondensation forms titanium dioxide, so adopt methyl ethyl diketone or methyl aceto acetate to make it form inner complex among the present invention,, lost efficacy to prevent the interpolation process in order that reduce its hydrolytie polycondensation speed.And the alkyl titanium oxide inner complex decomposes in the high temperature grafting, restores alkyl titanium oxide, and it and alkyl trimethoxysilane have collaborative sealing crosslinked between the alkenyl alkoxy silane grafts of preventing, make grafted material that good processibility and secular package stability be arranged.
Described alkyl trimethoxysilane is one of following or the mixture of two or more arbitrary proportion wherein: 1. methyltrimethoxy silane, 2. ethyl trimethoxy silane, 3. propyl trimethoxy silicane.
Described radical initiator can produce free radical on the sub polyethylene subchain under reaction conditions, can be one of following or the mixture of two or more arbitrary proportion wherein: 1. dicumyl peroxide, 2. t-butyl peroxide, the 3. peroxidation lauric acid tert-butyl ester.Be preferably dicumyl peroxide.
Described crosslinking catalyst is one of following or the mixture of two or more arbitrary proportion wherein: 1. dibutyl tin laurate, 2. toxilic acid dibutyl tin, 3. lauric acid toxilic acid dibutyl tin, 4. Bis(lauroyloxy)dioctyltin.Be preferably dibutyl tin laurate.
Described method is as follows: will dissolve in by the radical initiator of grafted material formula ratio in alkenyl alkoxy silane, alkyl trimethoxysilane and the alkyl titanium oxide inner complex mixture, mix with polyvinyl resin then, advance forcing machine in 120～180 ℃ of fusion-grafting granulations, the oven dry sealing is preserved; To mix by product aqua, crosslinking catalyst, the polyvinyl resin of catalysing material formula ratio, advance forcing machine in 120～160 ℃ of melt pelletization, the oven dry sealing is preserved; Grafted material is mixed by 10: 1 mass ratioes with catalysing material, advance forcing machine and under 155～165 ℃, extrude, carry out crosslinkedly under field conditions (factors), promptly get described crosslinked polyethylene.
Preferably, it is composed as follows to prepare the raw materials quality of described crosslinked polyethylene:
Grafted material:
100 parts of low density polyethylenes
2 parts of vinyltriethoxysilanes
1.5 parts of methyltrimethoxy silanes
1.5 parts of four titanium butoxide and ethyl acetoacetate chelates
0.2 part of radical initiator dicumyl peroxide
Catalysing material:
100 parts of low density polyethylenes
Produce 10 parts of aqua terpolycyantoamino-formaldehyde resins
2 parts of crosslinking catalyst dibutyl tin laurates;
Described method is as follows:
By above-mentioned formula ratio, the initiator dicumyl peroxide is dissolved in the mixture of vinyltriethoxysilane, methyltrimethoxy silane, four titanium butoxide and ethyl acetoacetate chelate, mix with low density polyethylene then, advance forcing machine 170 ℃ of fusion-grafting granulations, the oven dry sealing is preserved; Product aqua terpolycyantoamino-formaldehyde resin, crosslinking catalyst dibutyl tin laurate, the low density polyethylene of formula ratio are mixed, advance forcing machine 130 ℃ of melt pelletization, the oven dry sealing is preserved; Grafted material is mixed by mass ratio with catalysing material at 10: 1, advance forcing machine and about 160 ℃, extrude, carry out crosslinkedly under the room temperature, promptly get described crosslinked polyethylene.
The method of preparing silane crosslinked polyethylene by room temperature crosslinking of the present invention, compared with prior art, technology advanced person, product yield height, energy consumption is low, and product performance are good, cost is low, have easy to process, raw material easily to store again, characteristics such as the product mechanical strength is big have bigger implementary value and economic results in society.
(4) description of drawings
Fig. 1 is different influences of producing aqua to the organosilane crosslinked polyethylene melt torque; 1: do not have the aqua of producing, 2: the product aqua is ZnO, 1: 1 mixture of stearic acid mass ratio, and 3: the product aqua is HCOONa2H
2O, 4: the product aqua is NaH
2PO
32H
2O, 5: producing aqua is the terpolycyantoamino-formaldehyde resin powder.Fig. 2 produces the influence of aqua sodium formiate to the silane grafted polyethylene melt torque for different amounts; 1: do not have the aqua of producing, 2: producing the aqua consumption is 0.5g, and 3: producing the aqua consumption is 1.0g, and 4: producing the aqua consumption is 1.5g, and 5: producing the aqua consumption is 2.0g, and 6: producing the aqua consumption is 4.0g.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1: different polyvinyl resins are to the influence of percentage of grafting
0.3 gram initiator dicumyl peroxide (DCP) is dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of 3 gram vinyltriethoxysilanes, 1 gram ethyl trimethoxy silane, 1 gram four titanium butoxide and methyl aceto acetate, again with 100 the gram different models the polyvinyl resin mixing, advance forcing machine 160 ℃ of fusion-grafting granulations, 80 ℃ the baking 1 hour the sealing preserve grafted material; Get grafted material 1 gram and wrap, put into the reaction flask of taking back flow condenser that is added with the 100ml trichloromethane, reflux 8 hours with filter paper, changed trichloromethane once in per 4 hours, and finished the back and take out filter paper packet, weigh after the oven dry, calculate percentage of grafting, the silane percentage of grafting of different polyvinyl resins sees Table 1:
Table 1: different polyvinyl resins are to the influence of percentage of grafting
| Polyvinyl resin | LDPE | LLDPE | HDPE | EVA |
| Percentage of grafting, % | 2.29 | 2.58 | 1.81 | 2.12 |
Embodiment 2: different alkenyl alkoxy silanes is to the influence of polycthylene grafted rate
0.1 gram initiator dicumyl peroxide (DCP) is dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of the different alkenyl alkoxy silane of 5 grams and 1.5 gram propyl trimethoxy silicanes, 1.5 gram four titanium butoxide and methyl ethyl diketone, again with 100 gram LLDPE mixings, advance forcing machine 160 ℃ of fusion-grafting granulations, 80 ℃ the baking 1 hour the sealing preserve grafted material; Getting grafted material 1 gram wraps with filter paper, put into the reaction flask of taking back flow condenser that is added with the 100ml trichloromethane, reflux 8 hours, changed trichloromethane once in per 4 hours, finish the back and take out filter paper packet, weigh after the oven dry, calculate percentage of grafting, different alkenyl alkoxy silanes see Table 2 at the percentage of grafting of LLDPE:
Table 2: different alkenyl alkoxy silanes are to the influence of polycthylene grafted rate
| Alkenyl alkoxy silane | The methacryloxypropyl triethoxyl silane | Vinyltriethoxysilane | The propenyl triethoxyl silane |
| Percentage of grafting, % | 3.56 | 4.73 | 4.33 |
Embodiment 3: the inner complex of methyltrimethoxy silane and four titanium butoxide and methyl aceto acetate is to the influence of the gel content of silane grafted polyethylene
0.1 gram initiator dicumyl peroxide (DCP) is dissolved in the mixed solution of the inner complex (methyltrimethoxy silane and four titanium butoxide inner complex mass ratioes 1: 1) of the methyltrimethoxy silane of 3 gram vinyltriethoxysilanes and different amounts and four titanium butoxide and methyl aceto acetate, again with 100 gram LDPE mixings, advance forcing machine 170 ℃ of fusion-grafting granulations, 80 ℃ the baking 1 hour the sealing preserve grafted material; Getting grafted material 1 gram wraps with filter paper, put into the reaction flask of taking back flow condenser that is added with 100ml toluene, reflux 8 hours, changed toluene once in per 4 hours, finish the back and take out filter paper packet, weigh after the oven dry, calculated for gel content, the gel content of the crosslinked with silicane LDPE that inner complex (mass ratio 1: the 1) consumption of different methyltrimethoxy silanes and four titanium butoxide and methyl aceto acetate makes sees Table 3: by data in the table as can be known, the inner complex consumption increase of methyltrimethoxy silane and four titanium butoxide and methyl aceto acetate can prevent the crosslinked of grafted material, and grafted material is crosslinked excessive, be that gel content is too high, will influence the processibility and the package stability of grafted material.
Table 3: different methyltrimethoxy silane consumptions are to the influence of crosslinked with silicane LDPE gel content
| The inner complex consumption of methyltrimethoxy silane and four titanium butoxide and methyl aceto acetate, g | 1.0 | 2.0 | 3.0 | 4.0 |
| Gel content, wt% | 59.6 | 47.8 | 36.7 | 28.4 |
Embodiment 4: different initiators is to the influence of organosilane crosslinked polyethylene gel content
The different initiators of 0.5 gram are dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of 2 gram vinyltriethoxysilanes and 1 gram propyl trimethoxy silicane, 1 gram four titanium butoxide and methyl aceto acetate, again with 100 gram LDPE mixings, advance forcing machine 180 ℃ of fusion-grafting granulations, 80 ℃ the baking 1 hour the sealing preserve grafted material; With the SODIUM PHOSPHATE, MONOBASIC that 30 grams produce aqua band crystal water, 3 gram catalyzer Bis(lauroyloxy)dioctyltins advance forcing machine 130 ℃ of melt pelletization with 100 gram LDPE, 80 ℃ of bakings sealed in 1 hour preserve catalysing material; Get 1000 gram grafted materials and 100 gram catalysing material mixings, advance forcing machine about 160 ℃, extrude finished product, sealing is preserved, and gets finished product material 1 gram and wraps with filter paper, puts into the reaction flask of taking back flow condenser that is added with 100ml toluene, reflux 8 hours, changed toluene once in per 4 hours, and finished the back and take out filter paper packet, weigh after the oven dry, calculated for gel content, the gel content of the crosslinked with silicane LDPE that different initiators make sees Table 4:
Table 4: different initiators are to the influence of crosslinked with silicane LDPE gel content
| Initiator | Dicumyl peroxide | T-butyl peroxide | The peroxidation lauric acid tert-butyl ester |
| Gel content, wt% | 35.6 | 32.8 | 33.2 |
Embodiment 5: initiator amount is to the influence of organosilane crosslinked polyethylene gel content
The different amounts initiator DCP is dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of 4 gram vinyltriethoxysilanes and 2 gram methyltrimethoxy silanes, 2 gram four titanium butoxide and methyl aceto acetate, again with 100 gram LDPE mixings, advance forcing machine 170 ℃ of fusion-grafting granulations, 80 ℃ the baking 1 hour the sealing preserve grafted material; The sodium-acetates of 20 gram band crystal water are produced aqua, and 2 gram catalyzer lauric acid toxilic acid dibutyl tins advance forcing machine 140 ℃ of melt pelletization with 100 gram LDPE, 80 ℃ of bakings sealed in 1 hour preserve catalysing material; Get 1000 gram grafted materials and 100 gram catalysing material mixings, advance forcing machine about 160 ℃, extrude finished product, sealing is preserved, and gets finished product material 1 gram and wraps with filter paper, puts into the reaction flask of taking back flow condenser that is added with 100ml toluene, reflux 8 hours, changed toluene once in per 4 hours, and finished the back and take out filter paper packet, weigh after the oven dry, calculated for gel content, the gel content of the crosslinked with silicane LDPE that different amount of initiator make sees Table 5:
Table 5: different initiator amounts are to the influence of crosslinked with silicane LDPE gel content
| DCP，g | 0.05 | 0.2 | 0.5 | 1.0 |
| Gel content, wt% | 37.8 | 47.6 | 62.3 | 65.2 |
Embodiment 6: produce the influence of aqua kind to the organosilane crosslinked polyethylene melt torque
0.1 gram initiator DCP is dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of 3 gram vinyltriethoxysilanes and 1.5 gram methyltrimethoxy silanes, 1.5 gram four titanium butoxide and methyl aceto acetate, again with 100 gram LDPE mixings, advance the HAAKE torque rheometer 160 ℃ of melting mixing 4 minutes, add the different aquas that produce of 1 gram, 0.2 gram catalyzer dibutyl tin laurate is measured melt torque and the change curve of time, see Fig. 1 for details, the cross-linking effect that aqua is produced in the big more explanation of change in torque is big more.
Embodiment 7: produce the influence of aqua consumption to the organosilane crosslinked polyethylene melt torque
1.0 gram initiator DCP are dissolved in the mixed solution of the inner complex (mass ratio 1: 1) of 3 gram vinyltriethoxysilanes and 1.5 gram methyltrimethoxy silanes, 1.5 gram four titanium butoxide and methyl aceto acetate, again with 100 gram LDPE mixings, advance the HAAKE torque rheometer 160 ℃ of melting mixing 4 minutes, add the sodium formiate (HCOONa2H of the product aqua band crystal water of different amounts
2O) and 0.1 gram catalyzer dibutyl tin laurate, measure melt torque and the change curve of time, see Fig. 2 for details, the big more explanation cross-linking effect of change in torque is big more.Adding the sample that mixed 3 minutes behind the product aqua carries out as the gel content determining among the embodiment 3, result such as table 6.The rule basically identical of table 6 gel content delta data and Fig. 2 change in torque data.
The different gel contents that produce the organosilane crosslinked polyethylene of aqua consumption of table 6.
| Produce the aqua consumption, |
0 | 0.5 | 1 | 1.5 | 2 | 4 |
| Gel content when just extruding, wt% | 21.8 | 40.9 | 51.0 | 70.6 | 72.6 | 66.7 |
| Room temperature (25 ℃) is placed 2 days gel content, wt% | 25.2 | 62.3 | 68.6 | 72.1 | 71.9 | 72.4 |
The presentation of results of embodiment 3 increases the inner complex (mass ratio 1: 1) of saturated alkyl Trimethoxy silane and four titanium butoxide and methyl aceto acetate, helps the minimizing of gel content in the thiazolinyl silane oxide grafted material, thereby helps processing.The presentation of results of embodiment 5 too much uses initiator DCP when the inner complex consumption of certain saturated alkyl Trimethoxy silane and four titanium butoxide and methyl aceto acetate, can make the gel content of crosslinked material excessive equally, and is not easy to processing.The presentation of results of embodiment 7 adds the product aqua and helps normal temperature crosslinked speed to increase, and crosses the consumption of volume production aqua, is unfavorable for processing.
Claims (1)
1. the method for a preparing silane crosslinked polyethylene by room temperature crosslinking, the raw materials quality that it is characterized in that preparing described crosslinked polyethylene is composed as follows:
Grafted material:
100 parts of low density polyethylenes
2 parts of vinyltriethoxysilanes
1.5 parts of methyltrimethoxy silanes
1.5 parts of four titanium butoxide and ethyl acetoacetate chelates
0.2 part of radical initiator dicumyl peroxide
Catalysing material:
100 parts of low density polyethylenes
Produce 10 parts of aqua terpolycyantoamino-formaldehyde resins
2 parts of crosslinking catalyst dibutyl tin laurates;
Described method is as follows:
Grafted material preparation: by above-mentioned formula ratio, the initiator dicumyl peroxide is dissolved in the mixture of vinyltriethoxysilane, methyltrimethoxy silane, four titanium butoxide and ethyl acetoacetate chelate, mix with low density polyethylene then, advance forcing machine 170 ℃ of fusion-grafting granulations, the oven dry sealing is preserved;
The catalysing material preparation: product aqua terpolycyantoamino-formaldehyde resin, crosslinking catalyst dibutyl tin laurate, the low density polyethylene of formula ratio are mixed, advance forcing machine 130 ℃ of melt pelletization, the oven dry sealing is preserved;
Crosslinked polyethylene preparation: grafted material is mixed by mass ratio with catalysing material at 10: 1, advance forcing machine and extrude, carry out crosslinkedly under the room temperature, promptly get described crosslinked polyethylene at 160 ℃.
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| CN1900130A (en) | 2007-01-24 |
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Assignee: Jiangsu automobile decoration Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2011320000987 Denomination of invention: Process for preparing silane crosslinked polyethylene by room temperature crosslinking Granted publication date: 20090204 License type: Exclusive License Open date: 20070124 Record date: 20110713 |
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