CN101580680B - 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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- CN101580680B CN101580680B CN2009100382128A CN200910038212A CN101580680B CN 101580680 B CN101580680 B CN 101580680B CN 2009100382128 A CN2009100382128 A CN 2009100382128A CN 200910038212 A CN200910038212 A CN 200910038212A CN 101580680 B CN101580680 B CN 101580680B
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 38
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 35
- -1 polyethylene Polymers 0.000 title claims abstract description 35
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title 1
- 229920000098 polyolefin Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 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 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 2
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical class CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract description 2
- 230000006353 environmental stress Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
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 to30 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 o ne-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, like container inside lining, water heater liner and pipeline inside and outside coating etc.
Technical background
Vilaterm is the most important derived product of ethene, accounts for 70% of world's polyolefine consumption, and excellent property has nonpoisonous and tasteless; Raw material is cheap, and lower temperature resistance is good, and water-absorbent is low; Excellent chemicalstability is arranged, various pharmaceutical chemicalss such as salt tolerant acid, hydrofluoric acid, amine, sodium hydroxide, Pottasium Hydroxide under the room temperature, still; Vilaterm non-refractory, the maximum operation (service) temperature of new LDPE (film grade) are 60 ℃, and the high density polyethylene(HDPE) maximum operation (service) temperature also can only reach 70 ℃.
Vilaterm is after crosslinked; The over-all propertieies such as mechanical property, environmental stress cracking resistance, resistance to corrosive chemicals ability, 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 temperature tolerance and the weathering resistance of hot melt adhesive 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 processing 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 possibly exist and disperse uneven problem.
00109087.9 pair of Vilaterm of another Chinese patent carries out carrying out fusion-grafting after the preparatory radiation; Functional polyethylene that obtains and metal, pottery, adhesivepropertieies such as glass are good; Because the Vilaterm 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. Dowcorning 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 chemicalstability, 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 objective of the invention is to realize 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 Vilaterm, 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 Vilaterm 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 Vestolen PP 7052, PS; 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, for example Diisopropyl azodicarboxylate; Lucidol, Di Cumyl Peroxide 99, di-t-butyl peroxide, 1; 1 '-two (t-butylperoxy)-3,3,5 trimethyl-cyclohexanes; 2, one or more mixing in 5-dimethyl-(peroxo--2, the 5-di-t-butyl) hexane.Preferred Di Cumyl Peroxide 99.
Above-mentioned crosslinkable polyethylene hot-melt adhesive composition; Described silane coupling agent is a vinyltrimethoxy silane; Vinyltriethoxysilane; N-(beta-aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, 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 verivate thereof, methyl acrylic ester and the SY-Monomer G.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 through 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 said 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.
Advantages such as the present invention has combined the good and crosslinked polyethylene stable performance of polyethylene hot-melt adhesive adhesive property, and temperature tolerance is good are in bonding process; This hot melt adhesive fully soaks into, and can reach cohesive strength preferably, and can solidify rapidly; Suction takes place crosslinkedly under state of nature, and 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; Improved the temperature tolerance and the chemicalstability 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 done further elaboration through concrete embodiment, but scope of the present invention is not limited to this specific examples.
Embodiment 1～8
Vilaterm and other polyolefine are added polar monomer, silane coupling agent, initiator and other auxiliary agents; After weighing, drop into mixing machine mixed at high speed 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 temperature, 180～190 ℃ of two district 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 expect the bar depanning after water cooling, and air blast dries up pelletizing afterwards 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 Vilaterm A is a linear low density polyethylene, and Vilaterm B is a high density polyethylene(HDPE), and Vilaterm 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 Di Cumyl Peroxide 99.
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 (8)
1. crosslinkable polyethylene hot-melt adhesive composition, its prescription comprises following component with listed as parts by weight:
Wherein, Described Vilaterm is more than one 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, and described other polyolefine comprise Vestolen PP 7052, PS; More than one mixing in the ethene copolymer, its melt flow rate(MFR) are 0.5～50g/10min.
2. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described initiator is selected from more than one mixing in superoxide, the azo-initiator.
3. crosslinkable polyethylene hot-melt adhesive composition according to claim 1; It is characterized in that: described initiator is selected from Diisopropyl azodicarboxylate, Lucidol, Di Cumyl Peroxide 99, di-t-butyl peroxide, 1; 1 '-two (t-butylperoxy)-3,3,5 trimethyl-cyclohexanes, 2; More than one mixing in 5-dimethyl-(peroxo--2, the 5-di-t-butyl) hexane.
4. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described silane coupling agent is more than one mixing in vinyltrimethoxy silane, vinyltriethoxysilane, N-(beta-aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl trimethoxy silicane, the γ-An Jibingjisanyiyangjiguiwan.
5. crosslinkable polyethylene hot-melt adhesive composition according to claim 1 is characterized in that: described polar monomer is selected from more than one mixing in toxilic acid (acid anhydride) and ester class, vinylformic acid and ester class thereof, vinylbenzene, the methyl acrylic ester.
6. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-5 is extruded through the single stage method reaction and to be obtained.
7. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-5, the precrosslink degree before the construction be below 10%, and degree of crosslinking is 30%～70% after full cross-linked.
8. the described crosslinkable polyethylene hot-melt adhesive composition of arbitrary claim among the claim 1-5 is applied to material adhesive, or is applied to container inside lining and pipeline coatings.
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| CN2009100382128A CN101580680B (en) | 2009-03-27 | 2009-03-27 | Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof |
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| CN101580680B true CN101580680B (en) | 2012-02-15 |
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Families Citing this family (18)
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| CN101805424B (en) * | 2010-03-12 | 2012-01-04 | 金发科技股份有限公司 | Silane crosslinked polyethylene special-purpose material for internal bladder of electric water heater |
| CN102181239B (en) * | 2011-01-26 | 2013-06-12 | 江门市丁氏粘合剂实业有限公司 | Formaldehyde-free film adhesive and method for manufacturing veneer board and homodromous laminated material |
| CN102260471A (en) * | 2011-04-02 | 2011-11-30 | 安徽金门工贸有限公司 | Method for making hot melt adhesive |
| CN103963135A (en) * | 2013-01-31 | 2014-08-06 | 戴武兵 | Formaldehyde-free fiber material and formation method thereof, as well as fiber decorative material and manufacturing method thereof |
| CN104403580A (en) * | 2014-11-04 | 2015-03-11 | 张桂华 | Multi material adhesive used for transporting tape |
| JPWO2017098889A1 (en) * | 2015-12-07 | 2018-07-26 | 株式会社Moresco | Hot-melt composition, method for producing hot-melt composition, sealing material, electronic device, and lamp |
| WO2017098890A1 (en) * | 2015-12-07 | 2017-06-15 | 株式会社Moresco | Hot melt composition, hot melt composition production method, seal material, electronic device, and lamp |
| TW201829685A (en) * | 2017-02-09 | 2018-08-16 | 汪毓傑 | Hot-melt adhesive film for bonding rubber and EVA foaming materials capable of greatly reducing the manufacturing cost of shoe sole |
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| CN108531016A (en) * | 2018-04-23 | 2018-09-14 | 石磊 | A kind of preparation method of water-proof acrylic acid paint |
| CN110295019B (en) * | 2019-06-13 | 2020-11-10 | 江苏鸿硕工程塑料科技股份有限公司 | Polyethylene pipe bonding material and preparation method thereof |
| CN111394026A (en) * | 2019-12-31 | 2020-07-10 | 宁波能之光新材料科技股份有限公司 | Adhesive resin for high-adhesion wood-plastic aluminum plate and one-step preparation method thereof |
| CN113912918A (en) * | 2020-07-10 | 2022-01-11 | 国家能源投资集团有限责任公司 | Crosslinkable polyethylene compositions, crosslinkable polyethylene blends and composite articles |
| CN113915423A (en) * | 2020-07-10 | 2022-01-11 | 国家能源投资集团有限责任公司 | Anticorrosion Pipes and Applications |
| CN112768844B (en) * | 2021-01-12 | 2023-03-24 | 天津市捷威动力工业有限公司 | Long-lasting tab and application |
| CN114149772B (en) * | 2021-11-25 | 2023-04-18 | 广州番禺电缆集团有限公司 | Hot melt adhesive for crosslinked polyethylene cable connector and preparation method thereof |
| CN114213107A (en) * | 2021-12-30 | 2022-03-22 | 武汉理工大学 | A 3D printing molding method based on ceramic materials |
| CN115627132B (en) * | 2022-12-19 | 2023-03-21 | 广州鹿山新材料股份有限公司 | Conductive adhesive material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317529A (en) * | 2001-04-02 | 2001-10-17 | 广州市鹿山化工材料有限公司 | Adhesive for coating on steel pipe |
| CN1338496A (en) * | 2001-04-30 | 2002-03-06 | 中国兵器工业第五三研究所 | Composition, preparation method and application of hot melt adhesive |
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