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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- CN100457798C CN100457798C CNB2006100525202A CN200610052520A CN100457798C CN 100457798 C CN100457798 C CN 100457798C CN B2006100525202 A CNB2006100525202 A CN B2006100525202A CN 200610052520 A CN200610052520 A CN 200610052520A CN 100457798 C CN100457798 C CN 100457798C
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- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 239000004718 silane crosslinked polyethylene Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 20
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 20
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 20
- 239000004702 low-density polyethylene Substances 0.000 claims description 20
- 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 description 18
- 239000000203 mixture Substances 0.000 claims description 16
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical class CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 14
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical class CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- -1 alkenyl alkoxy silane Chemical compound 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 229910000077 silane Inorganic materials 0.000 abstract description 14
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 229920013716 polyethylene resin Polymers 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 150000001282 organosilanes Chemical class 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WJXKWIFHRZWPET-UHFFFAOYSA-N tert-butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC(C)(C)C WJXKWIFHRZWPET-UHFFFAOYSA-N 0.000 description 2
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- OHRZBWUOCCQYST-UHFFFAOYSA-N ethenyl(triethoxy)silane;3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)C=C.CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C OHRZBWUOCCQYST-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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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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| EP4253437A1 (en) * | 2022-03-28 | 2023-10-04 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Silane-based crosslinking mixture and method for crosslinking thermoplastic polymers |
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