CN101580680A - Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof - Google Patents
Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a crosslinkable polyethylene hot-melt adhesive composition. The composition is prepared from the following components by weight portion: 60 to 92 portions of polyethylene, 8 to 30 portions of other polyolefin, 0.01 to 0.2 portion of evocating agent, 0.3 to 3 portions of silane coupling agent, 0.1 to 2 portions of polar monomer and 0.1 to 5 portions of auxiliary agent by a one-step method. The crosslinkable polyethylene hot-melt adhesive composition has the characteristics of high bonding strength, ideal temperature tolerance, excellent chemical resistance and good environmental stress cracking resistance, and can be widely used in metal-plastic bonding under severe conditions requiring temperature tolerance and acid and alkali resistance; meanwhile, the composition can also be pulverized so as to be used as inside and outside container coat such as container inner lining, water heater tank, inside and outside pipeline coat and the like.
Description
Technical field
This paper relates to a kind of polyethylene hot-melt adhesive product, particularly a kind of crosslinkable polyethylene hot-melt adhesive that can be used under the severe condition such as heatproof or chemical-resistant resistance, be used as the container inside and outside coating after also can wearing into simultaneously powder, as container inside lining, water heater liner and pipeline inside and outside coating etc.
Technical background
Polyethylene is the most important derived product of ethene, accounts for 70% of world's polyolefine consumption, excellent property, have nonpoisonous and tasteless, raw material is cheap, and lower temperature resistance is good, and water-absorbent is low, excellent chemical stability is arranged, various pharmaceutical chemicalss such as salt tolerant acid, hydrofluoric acid, amine, sodium hydroxide, potassium hydroxide under the room temperature, still, the polyethylene non-refractory, the maximum operation (service) temperature of new LDPE (film grade) is 60 ℃, and the high density polyethylene(HDPE) maximum operation (service) temperature also can only reach 70 ℃.
Polyethylene is after crosslinked, the over-all propertieies such as mechanical property, environmental stress cracking resistance, resistance to corrosive chemicals energy, creep resistance and electrical property of PE have not only been significantly improved, and improved temperature resistant grade very significantly, the heat resisting temperature that can make PE is brought up to more than 100 ℃ from 70 ℃, thereby has widened the range of application of PE greatly.
The polyethylene crosslinking technology is applied to the hot melt adhesive field, and degree of crosslinking rises in the abundant bonding back of polyethylene hot-melt adhesive and base material, has both helped providing the bonding strength and the stability of this hot melt adhesive, and the while also can be improved the temperature tolerance of hot melt adhesive and weathering resistance etc.
Chinese patent 200510116675 has been introduced a kind of reaction polyolefin type hot melt-adhesive.Mainly form by response type polyolefine (the unformed polyolefine of siloxanes grafting), tackifier and catalyzer, there is following problem in this hot melt adhesive: 1. tackifier use too much, then surface viscosity is bigger, and processing and storage be difficulty, and more then bounding force is relatively low in use; 2 curing speeds are slower, and initial bonding strength is lower relatively.
Chinese patent 03150344.6 has been introduced a kind of polyolefin compositions of high-temperature resistant anti-corrosive, because said composition comprises the silane graft polyolefin, the polarity polymer, therefore need to divide several steps to produce, complex process, and the silane graft polyolefin of making very easily absorbs water crosslinked in storage process, influence end properties, simultaneously, the effect that part has been served as filler in the finished product production process of silane graft polyolefin may exist and disperse uneven problem.
00109087.9 pair of polyethylene of another Chinese patent carries out carrying out fusion-grafting after the pre-radiation, functional polyethylene that obtains and metal, pottery, adhesivepropertieies such as glass are good, because the polyethylene temperature tolerance is lower, therefore the use temperature of this functional polyethylene material is limited, and chemical resistance and intensity are general, can not be used as container inside lining.
In addition, about poly crosslinked, develop the comparatively sophisticated following two kinds of methods that have at present, a kind of is the two-step approach of U.S. Dowcoming company exploitation, is called the Sioplas method, and another kind is the single stage method of Switzerland Nokia-Maillefer company exploitation, it is the Monoail method, the crosslinked polyethylene that two kinds of methods obtain can reach very high (degree of crosslinking more than 80%), have good temperature tolerance and chemical stability, but this material does not have adhesiveproperties.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of hot-melt adhesive composition, both had the high bond strength of polyethylene hot-melt adhesive, have high temperature resistant, the chemical resistance excellent characteristics of crosslinked polyethylene again.
The object of the present invention is achieved like this: a kind of crosslinkable polyethylene hot-melt adhesive composition, its prescription comprises following component with listed as parts by weight: 60～92 parts of polyethylene, 8～30 parts of other polyolefine, 0.01～0.2 part of initiator, 0.3～3 part of silane coupling agent, 0.1～2 part of polar monomer, 0.1～5 part of auxiliary agent.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, described polyethylene is one or more composite the forming in high-pressure polyethylene, high density polyethylene(HDPE) and the linear low density polyethylene, its melt flow rate (MFR) is 0.1～60g/10min, preferred 3～50g/10min, most preferably 5～30g/10min.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, described other polyolefine comprise polypropylene, polystyrene, ethene copolymer, one or more mixing in the ethylene-propylene copolymer, its melt flow rate (MFR) are 0.5～50g/10min, preferred 3～20g/10min.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, described initiator is selected from superoxide and/or azo-initiator, Diisopropyl azodicarboxylate for example, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1 '-two (t-butylperoxy)-3,3,5 trimethyl-cyclohexanes, 2, one or more mixing in 5-dimethyl (peroxidation-2, the 5-di-t-butyl) hexane.Preferred dicumyl peroxide.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, described silane coupling agent is a vinyltrimethoxy silane, vinyltriethoxysilane, N-(beta-aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, one or more mixing in the γ-An Jibingjisanyiyangjiguiwan.The preferred vinyl Trimethoxy silane.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, described polar monomer are selected from any one or more blended combinations in toxilic acid (acid anhydride) and ester class, vinylformic acid and ester class, vinylbenzene and derivative thereof, methyl acrylic ester and the glycidyl methacrylate.Preferred toxilic acid (acid anhydride) and ester class thereof.
Above-mentioned auxiliary agent adds according to actual needs, for example oxidation inhibitor, catalyzer etc.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, this hot melt adhesive are extruded by the single stage method reaction and are obtained, and can reach more than the 100N/25mm the bonding strength of metal.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, the precrosslink degree before described this hot melt adhesive construction is below 10%, and is preferred below 5%.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition, crosslinking rate is 30%～70% after full cross-linked.
The present invention combines the good and crosslinked polyethylene stable performance of polyethylene hot-melt adhesive adhesive property, advantages such as temperature tolerance is good, in bonding process, this hot melt adhesive fully soaks into, can reach cohesive strength preferably, and can solidify rapidly, suction takes place crosslinked under state of nature, hot melt adhesive is inner and form the reticulated structure of chemical bond with the interface of base material, has not only improved bounding force, has improved the temperature tolerance and the chemical stability of hot melt adhesive simultaneously, therefore, this hot melt adhesive can be applicable to the material adhesive under the severe condition, simultaneously, also can be used for various fields such as container inside lining and pipeline coatings.
Embodiment
Below come the present invention is further elaborated by specific embodiment, but scope of the present invention is not limited to this specific examples.
Embodiment 1～8
Polyethylene and other polyolefine are added polar monomer, silane coupling agent, initiator and other auxiliary agents, after weighing, drop into mixing machine high-speed mixing 3～5min, put into then in the TE35 twin screw extruder (length-to-diameter ratio is 40: 1), 160 ℃ of control forcing machine one district's temperature, 180～190 ℃ of two district's temperature, 190～200 ℃ of three district's temperature, 200～210 ℃ of four to seven district's temperature, 200～210 ℃ of die head temperatures, 195～205 ℃ of melt temperatures, screw speed 30r/min, material bar depanning is after water cooling, air blast dries up the back pelletizing and obtains product, test its performance, concrete experimental formula and test result such as table 1.
Table 1. embodiment 1～8 prescription and test result
Annotate: melting index is tested with reference to GB/T3682; Stripping strength is tested with reference to GB-T2791, and degree of crosslinking is tested with reference to GB/T18992.
Above-mentioned polyethylene A is a linear low density polyethylene, and polyethylene B is a high density polyethylene(HDPE), and polyethylene C is a new LDPE (film grade), and its melt flow rate (MFR) is 0.1～60g/10min, preferred 3～50g/10min, most preferably 5～30g/10min.
Said polyolefins D is an ethylene-propylene copolymer, and polyolefine E is ethene-α octene copolymer, and its melt flow rate (MFR) is 0.5～50g/10min, preferred 3～20g/10min.
Above-mentioned initiator is a dicumyl peroxide.
Above-mentioned coupling agent A is a vinyltriethoxysilane, and coupling agent B is a vinyltrimethoxy silane.
Above-mentioned polar monomer is a maleic anhydride.
Above-mentioned auxiliary agent is mainly oxidation inhibitor and catalyzer, and for example adopting oxidation inhibitor is 168,1010, and catalyzer is a dibutyltin dilaurate catalyst.
Claims (10)
1. crosslinkable polyethylene hot-melt adhesive composition, its prescription comprises following component with listed as parts by weight:
60～92 parts of polyethylene
8～30 parts of other polyolefine
0.01～0.2 part of initiator
0.3～3 part of silane coupling agent
0.1～2 part of polar monomer
0.1～5 part of auxiliary agent.
2. crosslinkable polyethylene hot-melt adhesive composition according to claim 1, it is characterized in that: described polyethylene is one or more composite the forming in high-pressure polyethylene, high density polyethylene(HDPE) and the linear low density polyethylene, its melt flow rate (MFR) is 0.1～60g/10min, preferred 3～50g/10min, most preferably 5～30g/10min.
3. crosslinkable polyethylene hot-melt adhesive composition according to claim 1, it is characterized in that: described other polyolefine comprise polypropylene, polystyrene, ethene copolymer, one or more mixing in the ethylene-propylene copolymer, its melt flow rate (MFR) are 0.5～50g/10min.
4. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described initiator is selected from one or more mixing in superoxide, the azo-initiator.
5. crosslinkable polyethylene hot-melt adhesive composition according to claim 1, it is characterized in that: described initiator is selected from Diisopropyl azodicarboxylate, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1 '-two (t-butylperoxy)-3,3,5 trimethyl-cyclohexanes, 2, one or more mixing in 5-dimethyl (peroxidation-2, the 5-di-t-butyl) hexane.
6. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described silane coupling agent is one or more mixing in vinyltrimethoxy silane, vinyltriethoxysilane, N-(beta-aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl trimethoxy silicane, the γ-An Jibingjisanyiyangjiguiwan.
7. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described polar monomer is selected from any one or more mixing in toxilic acid (acid anhydride) and ester class, vinylformic acid and ester class, vinylbenzene and derivative thereof, methyl acrylic ester and the glycidyl methacrylate.
8. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-7 is extruded by the single stage method reaction and to be obtained.
9. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-7, the precrosslink degree before the construction be below 10%, and degree of crosslinking is 30%～70% after full cross-linked.
10. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-7 is applied to material adhesive, or is applied to container inside lining and pipeline coatings.
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Denomination of invention: Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof Effective date of registration: 20140620 Granted publication date: 20120215 Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou branch Pledgor: Guangzhou Lushan New Materials Co., Ltd. Registration number: 2014990000490 |
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Effective date of registration: 20201109 Address after: 510700 No.22, Pubei Road, YUNPU Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Patentee after: GUANGZHOU LUSHAN NEW MATERIALS Co.,Ltd. Patentee after: Jiangsu Lushan New Material Co.,Ltd. Address before: 303, room 2, building 22, 510530 Pu Po Road North, Guangzhou, Whampoa, Guangdong Patentee before: GUANGZHOU LUSHAN NEW MATERIALS Co.,Ltd. |