CN102190984A - Hot-melt adhesive for steel-plastic composite pipe - Google Patents
Hot-melt adhesive for steel-plastic composite pipe Download PDFInfo
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- CN102190984A CN102190984A CN 201110087796 CN201110087796A CN102190984A CN 102190984 A CN102190984 A CN 102190984A CN 201110087796 CN201110087796 CN 201110087796 CN 201110087796 A CN201110087796 A CN 201110087796A CN 102190984 A CN102190984 A CN 102190984A
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Abstract
The invention discloses a hot-melt adhesive for a steel-plastic composite pipe, which is prepared by blending and extruding the following components in percentage by weight by a parallel double screw extruder: 5-40% of binding resin master batch, 50-80% of polyolefin resin, 5-25% of tackifying resin and 0.02-5% of inorganic rare-earth oxide, wherein the binding resin is prepared by carrying out graft modification on polyethylene and/or ethylene copolymer, which is/are used as the matrix resin, and initiator (accounting for 0.01-0.2 wt% of the binding resin master batch) and unsaturated polar monomer (accounting for 0.1-5 wt% of the binding resin master batch); the polyolefin resin is used for adjusting the consumption of the binding resin master batch and the comprehensive properties of the hot-melt adhesive; and the tackifying resin is one or combination of SBS (styrene-butadiene-styrene), SEBS (styrene-ethylene-butadiene-styrene), SIS (styrene-isoprene-styrene), cis-1,4-polybutadiene rubber, nitrile-butadiene rubber and natural rubber. Since the rare-earth oxide is added, the grafting ratio of the binding resin master batch in the hot-melt adhesive is increased, thereby obviously enhancing the initial viscosity, enduring viscosity, binding strength and other properties.
Description
Technical field
The present invention relates to a kind of copolymer adhesive, specifically a kind of hot melt adhesive especially a kind ofly is used for the hot melt adhesive that steel is moulded pipe.
Background technology
Steel-plastics composite pipe is fast-developing in recent years a kind of novel pipeline, and it is a matrix with steel pipe, steel band or Steel Skeleton, with various types of plastics (as polypropylene, polyethylene, polyvinyl chloride, nylon etc.) through being composited.Advantage such as it is the chemical resistance and the plastic pipe inner wall smooth that utilize the rigidity of metal and plastics, incrustation is few, fluid resistance is little.Therefore, steel-plastics composite pipe has obtained using widely in industrial and agricultural production and daily life and urban construction.
Steel-plastics composite pipe is made up of five-layer structure, and its composition is followed successively by from the inside to the outside: polyethylene/hot melt adhesive/steel pipe or steel band/hot melt adhesive/polyethylene.Olefin plastics is an apolar substance, if there is not the participation of hot melt adhesive, metal can't combine with olefin plastics.Hot melt adhesive not only has good consistency with olefin plastics such as polyethylene, and can realize the persistence bonding to steel band, therefore can obtain the ideal composite pipe by hot melt adhesive.This sandwich has great universality, for example serves as a contrast plastic-steel plastic composite, three PE, two PE steel-plastics composite pipes, aluminum-plastic laminated tube etc.
At the existing many patent reports of the compound sticking of metal and macromolecular material.Publication number is the Chinese patent of CN1323867A, discloses a kind of inorganic nano material modified hot melt adhesive, and it adds inorganic nano-particle CaCO
3, TiO
2, talcum powder or SiO
2Increase the adsorptivity and the lasting cohesive force of hot melt adhesive, aluminum pipe and vinyon effectively are bonded together, obtain the plastic-aluminum pipe matrix material of excellent property; But mould pipe a lot of limitation are arranged then if above-mentioned hot melt adhesive is applied to steel.Because steel is moulded pipe special Working environment and purposes, there is higher requirement aspects such as physical and mechanical properties, chemical resistance, ageing-resistant performance and processing characteristics to hot melt adhesive: aluminum-plastic laminated tube belongs to the small dimension composite pipe, cohesive strength to hot melt adhesive requires low, steel-plastics composite pipe is mainly used in big specification multiple-unit tube such as public works, natural gas line, and the cohesive strength of hot melt adhesive is had relatively high expectations; Therefore steel-plastics composite pipe is different with the mode of connection of plastic-aluminum pipe, and the hot melt adhesive strength of joint of above-mentioned patent is lower, when using it for steel-plastics composite pipe, situations such as hot melt adhesive ftractures, comes off appear in interface easily, thereby has reduced the overall performance that steel is moulded pipe.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of hot melt adhesive that is used for steel-plastics composite pipe, and its cohesive strength and mechanical property all can satisfy the requirement of steel-plastics composite pipe.
For addressing the above problem, the technical scheme that the present invention takes is as follows:
A kind of hot melt adhesive that is used for steel-plastics composite pipe, adopt parallel double-screw extruder to carry out blending technology by the component of following weight per-cent and extrude and form:
A, adhering resin masterbatch 5 ~ 40%, it is a matrix resin with polyethylene and/or ethylene copolymer, the unsaturated polar monomer that add to add the initiator that accounts for adhering resin masterbatch 0.01 ~ 0.2wt.% and 0.02 ~ 6wt.% carries out graft modification and forms;
B, polyolefin resin 50 ~ 80% are one or more compound in metallocene PE, new LDPE (film grade), high density polyethylene(HDPE) or the EVA resin;
C, tackifying resin 5 ~ 25%, be the SBS(styrene-butadiene-styrene block copolymer), the SEBS(polystyrene is end segment, the ethene-butylene copolymer that obtains with the polyhutadiene hydrogenation is the linearity three embedding multipolymers of middle elastomeric block), SIS(vinylbenzene-isoprene-styrene block copolymer), one or more compound of cis-1,4-polybutadiene rubber, paracril or natural rubber;
D, rare earth oxide 0.02 ~ 5 %.
In the above-mentioned composition, described matrix resin is: melting index is the high density polyethylene(HDPE) (HDPE) of 0.5 ~ 50g/10min; Melting index is the linear low density polyethylene (LLDPE) of 0.5 ~ 50g/10min; Perhaps ethylene copolymer is that the VA content of 18 ~ 450g/10min is 13 ~ 28% EVA resin as melting index.
Described initiator is benzoyl peroxide (BPO) and/or dicumyl peroxide (DCP).
Described unsaturated polar monomer is maleic anhydride and/or vinylformic acid, its content if＜0.02wt.% then cohesive force reduce, if unreacted unsaturated monomer that 6 wt.% are then unnecessary can produce variable color, gel, bubble, irritating smell etc., influences the long-term stability of final product quality.Preferred 0.05 ~ 5wt.%.
The preparation method of described adhering resin masterbatch: with one or more kinds of compound among described HDPE, LLDPE or the EVA is matrix resin, in matrix resin, add described initiator and unsaturated polar monomer, under 150 ~ 230 ℃ temperature, adopt parallel double-screw to extrude then, obtain the adhering resin masterbatch.
The ratio that described adhering resin masterbatch accounts for hot melt adhesive is 5 ~ 40%; If＜5%, then there is not cohesive force; If 40%, then cost rises and irritating smell is arranged; Preferred 20 ~ 30%.
By the ratio of adjusting various tackifying resins reach the initial bonding strength that strengthens the hot melt adhesive product, temperature resistant capability and with the seepage force on steel surface.If tackifying resin accounts for the hot melt adhesive gross weight and is higher than 30%, then softening temperature reduces, and mechanical property descends thereupon and its high thermal resistance weakens, with the consistency variation of olefine kind resin; If be lower than 5%, then do not have the effect of tackify.Described tackifying resin preferred proportion is 10 ~ 15%.
Described rare earth oxide is one or more in lanthanum trioxide, cerium oxide or the Neodymium trioxide.Preferred proportion is 1.5 ~ 2.0%.
Rare earth element has similar and unusual active chemical property; there is numerous tracks to can be used as the lone-pair electron that central ion is accepted ligand; rare earth ion has bigger ionic radius simultaneously; mainly form ion with inorganic or organic ligand and join key by electrostatic attraction; as the central atom of complex compound, often be 6 ~ 12 complex compound with multiple hydridization form formation such as d2sp3, d4sp3 or f3d5sp3 ligancy.Rare earth element excellent mechanical property and grouping principle thereof are all relevant with the geometric properties of rare earth element.Because atom and ionic radius are the important factors of physical propertiess such as decision crystalline configuration, hardness, density and fusing point, under normal temperature, condition of normal pressure, rare earth lanthanum, neodymium are two hexagonal crystallographic textures, and cerium is cubic system intensive (center of area) structure, when temperature, pressure change, most rare earth metal generation crystal conversions.
Hot melt adhesive preparation technology schema is seen Fig. 1, and actual conditions is as follows:
Under 150 ℃ ~ 230 ℃ temperature, adhering resin masterbatch, polyolefin resin, tackifying resin and rare earth oxide are prepared burden by the prescription requirement, after high-speed stirring is mixed, melt extrude through twin screw, can obtain being used for the hot melt adhesive of steel-plastics composite pipe then through common process such as pelletizing, screening, encapsulation.
With simultaneous test the improvement of the present invention to the hot melt adhesive performance is described below.
Referring to table 1, for the present invention adds the hot melt adhesive of different rare earth oxides and the test example and the performance comparison of not adding the hot melt adhesive of rare earth oxide.
Table 1 simultaneous test
Wherein, melting index (MI) characterizes flowing property, and softening temperature (TS) characterizes its resistance toheat, and 90 ℃ of stripping strengths (PS) characterize the adhesiveproperties of hot melt adhesive, tensile strength δ
tCharacterize the mechanical property of hot melt adhesive.As can be seen from Table 1, add the hot melt adhesive of rare earth element, the hot melt adhesive that its mechanical property and bonding strength are not added rare earth oxide significantly improves.
The beneficial effect that adopts technique scheme to produce is: the present invention mainly utilizes the unusual active chemical property of rare earth element; improve the over-all properties of hot melt adhesive; compare with the hot melt adhesive of hot melt adhesive that does not increase rare earth element and interpolation inorganic nano-particle, performances such as its mechanical property, resistance toheat, cohesive strength, weathering resistance, chemical resistance increase significantly: the tensile strength (δ that characterizes mechanical property
t)
,Reach 34MPa, softening temperature (TS) reaches 122 ℃, and 90 ℃ of stripping strengths (PS) reach 375 N/25mm; Hot melt adhesive of the present invention has significantly improved the quality of steel-plastics composite pipe, especially improves the resistance to impact shock and the ring stiffness of large-scale steel-plastic composite, water-drain pipeline, has increased the work-ing life of steel-plastics composite pipe.In the urbanization process of fast development, the hot melt adhesive of rare-earth oxide modified can be played a greater and greater role in the application of large-scale steel-plastic composite, water-drain pipeline.
Description of drawings
Fig. 1 is the preparation flow figure of hot melt adhesive of the present invention.
Embodiment
Embodiment 1
Under 150 ℃ ~ 230 ℃ temperature, adhering resin masterbatch, polyolefin resin, tackifying resin and rare earth oxide are prepared burden by table 2 and the specified weight part of table 3, after high-speed stirring is mixed then, melt extrude through twin screw, can obtain being used for the hot melt adhesive of steel-plastics composite pipe again according to common process through pelletizing, screening, packaging process.
The weight proportion of table 2 embodiment 1-7 each component
Annotate: cis-1,4-polybutadiene rubber described in the table 2 can replace with paracril or natural rubber.
Wherein the weight ratio of adhering resin masterbatch employing table 3 is prepared according to following step: add described initiator and unsaturated polar monomer in matrix resin, adopt parallel double-screw to extrude under 150 ~ 230 ℃ temperature, obtain the adhering resin masterbatch.
The proportioning of adhering resin masterbatch among the table 3 embodiment 1-7
Prepared hot melt adhesive carries out performance test, referring to table 4.As can be seen from Table 4, the hot melt adhesive tensile strength δ of present embodiment preparation
tFor
,30MPa, softening temperature (TS) is 117 ℃, 90 ℃ of stripping strengths (PS) are 350 N/25mm, satisfy the requirement of steel-plastics composite pipe to hot melt adhesive.
Embodiment 2 ~ 7
Repeat the method for embodiment 1 according to specified each component concentration in table 2 ~ 3.Listed test result at table 4.
The hot melt adhesive The performance test results that table 4 embodiment 1 ~ 7 is prepared
Claims (7)
1. a hot melt adhesive that is used for steel-plastics composite pipe adopts parallel double-screw extruder to carry out the blending technology extruding pelletization and forms, and it is characterized in that adopting the component of following weight per-cent to make:
A, adhering resin masterbatch 5 ~ 40%, it is a matrix resin with polyethylene and/or ethylene copolymer, the unsaturated polar monomer that add to add the initiator that accounts for adhering resin masterbatch 0.01 ~ 0.2wt.% and 0.02 ~ 6wt.% carries out graft modification and forms;
B, polyolefin resin 50 ~ 80% are one or more compound in metallocene PE, new LDPE (film grade), high density polyethylene(HDPE) or the EVA resin;
C, tackifying resin 5 ~ 25% are one or more compound of SBS, SEBS, SIS, cis-1,4-polybutadiene rubber, paracril or natural rubber;
D, rare earth oxide 0.02 ~ 5 %.
2. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 1 is characterized in that described rare earth oxide is one or more in lanthanum trioxide, cerium oxide or the Neodymium trioxide.
3. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 1 is characterized in that described initiator is benzoyl peroxide and/or dicumyl peroxide.
4. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 1 is characterized in that described unsaturated polar monomer is maleic anhydride and/or vinylformic acid, accounts for 0.05 ~ 5wt.% of adhering resin masterbatch.
5. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 1 is characterized in that described adhering resin masterbatch accounts for 20 ~ 30% of hot melt adhesive weight.
6. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 5 is characterized in that described tackifying resin accounts for 10 ~ 15% of hot melt adhesive gross weight.
7. the hot melt adhesive that is used for steel-plastics composite pipe according to claim 6 is characterized in that rare earth oxide accounts for 1.5 ~ 2.0% of hot melt adhesive gross weight.
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| CN2011100877965A CN102190984B (en) | 2011-04-08 | 2011-04-08 | Hot-melt adhesive for steel-plastic composite pipe |
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|---|---|---|---|
| CN2011100877965A CN102190984B (en) | 2011-04-08 | 2011-04-08 | Hot-melt adhesive for steel-plastic composite pipe |
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| CN102190984B CN102190984B (en) | 2012-11-14 |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102814A (en) * | 2013-01-28 | 2013-05-15 | 苏州井上高分子新材料有限公司 | EVA (ethylene-vinyl acetate) hot-melting adhesive and preparation method thereof |
| CN103173146A (en) * | 2013-03-19 | 2013-06-26 | 广州鹿山新材料股份有限公司 | Ultra-low temperature composite hot melt adhesive membrane for aluminum board and fireproof board and preparation method of composite hot melt adhesive membrane |
| CN103214994A (en) * | 2013-03-21 | 2013-07-24 | 马鞍山市中澜橡塑制品有限公司 | Hot melt adhesive with maleic anhydride grafted ethylene-ethyl acetate copolymer as main material and preparation method thereof |
| CN103468168A (en) * | 2013-08-13 | 2013-12-25 | 安徽东方金河精密机械制造有限公司 | Hot melt adhesive added with rare earth oxide |
| CN103509486A (en) * | 2013-09-06 | 2014-01-15 | 芜湖市正通电气设备有限公司 | Low-temperature-operable clean environment-friendly hot melt adhesive |
| CN103571378A (en) * | 2013-10-24 | 2014-02-12 | 芜湖众力部件有限公司 | Super weather-proof nano composite hot melt adhesive |
| CN103709974A (en) * | 2013-12-31 | 2014-04-09 | 广州市合诚化学有限公司 | Low-processing temperature adhesive resin as well as preparation method and application thereof |
| CN104497913A (en) * | 2014-12-16 | 2015-04-08 | 上海邦中高分子材料有限公司 | Binder resin for steel-plastic composite tube and preparation method of binder resin |
| CN105349073A (en) * | 2015-12-08 | 2016-02-24 | 河北金天塑胶新材料有限公司 | Hot melt adhesive used for winding plastic steel around water drain pipe and preparing method thereof |
| CN105778836A (en) * | 2016-04-14 | 2016-07-20 | 苏州隆芝耀新材料有限公司 | Amorphous block copolymer-modified polyvinyl adhesive |
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| CN106700974A (en) * | 2016-12-18 | 2017-05-24 | 钦州市科学技术开发中心 | Environmental-protection high-strength adhesive and preparation method thereof |
| CN107011838A (en) * | 2017-04-27 | 2017-08-04 | 安徽国登管业科技有限公司 | Steel plastic compount bonding material and preparation method thereof |
| CN107254024A (en) * | 2017-06-01 | 2017-10-17 | 安徽国登管业科技有限公司 | It is a kind of for adhering resin of steel-plastics composite pipe and preparation method thereof |
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| CN1323867A (en) * | 2001-06-13 | 2001-11-28 | 广州市鹿山化工材料有限公司 | Nanometer hot melt adhesive for aluminium-plastic tube |
| CN1401721A (en) * | 2002-09-06 | 2003-03-12 | 广州市鹿山化工材料有限公司 | Hot-melt polyolefin adhesive and composite structure film using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103102814A (en) * | 2013-01-28 | 2013-05-15 | 苏州井上高分子新材料有限公司 | EVA (ethylene-vinyl acetate) hot-melting adhesive and preparation method thereof |
| CN103173146A (en) * | 2013-03-19 | 2013-06-26 | 广州鹿山新材料股份有限公司 | Ultra-low temperature composite hot melt adhesive membrane for aluminum board and fireproof board and preparation method of composite hot melt adhesive membrane |
| CN103173146B (en) * | 2013-03-19 | 2015-03-04 | 广州鹿山新材料股份有限公司 | Ultra-low temperature composite hot melt adhesive membrane for aluminum board and fireproof board and preparation method of composite hot melt adhesive membrane |
| CN103214994A (en) * | 2013-03-21 | 2013-07-24 | 马鞍山市中澜橡塑制品有限公司 | Hot melt adhesive with maleic anhydride grafted ethylene-ethyl acetate copolymer as main material and preparation method thereof |
| CN103468168B (en) * | 2013-08-13 | 2016-03-23 | 安徽东方金河精密机械制造有限公司 | A kind of hot melt adhesive adding rare earth oxide |
| CN103468168A (en) * | 2013-08-13 | 2013-12-25 | 安徽东方金河精密机械制造有限公司 | Hot melt adhesive added with rare earth oxide |
| CN103509486A (en) * | 2013-09-06 | 2014-01-15 | 芜湖市正通电气设备有限公司 | Low-temperature-operable clean environment-friendly hot melt adhesive |
| CN103509486B (en) * | 2013-09-06 | 2016-03-30 | 芜湖市正通电气设备有限公司 | A kind of can the clean and environment-friendly hot melt adhesive of cold operation |
| CN103571378A (en) * | 2013-10-24 | 2014-02-12 | 芜湖众力部件有限公司 | Super weather-proof nano composite hot melt adhesive |
| CN103709974A (en) * | 2013-12-31 | 2014-04-09 | 广州市合诚化学有限公司 | Low-processing temperature adhesive resin as well as preparation method and application thereof |
| CN103709974B (en) * | 2013-12-31 | 2015-10-07 | 广州市合诚化学有限公司 | A kind of low processing temperature adhering resin and preparation method thereof and application |
| CN104497913A (en) * | 2014-12-16 | 2015-04-08 | 上海邦中高分子材料有限公司 | Binder resin for steel-plastic composite tube and preparation method of binder resin |
| CN105349073A (en) * | 2015-12-08 | 2016-02-24 | 河北金天塑胶新材料有限公司 | Hot melt adhesive used for winding plastic steel around water drain pipe and preparing method thereof |
| CN105778836A (en) * | 2016-04-14 | 2016-07-20 | 苏州隆芝耀新材料有限公司 | Amorphous block copolymer-modified polyvinyl adhesive |
| CN106010429A (en) * | 2016-05-26 | 2016-10-12 | 鄂州市兴欣建材有限责任公司 | Polyethylene hot melt adhesive and preparation method and application thereof |
| CN106010429B (en) * | 2016-05-26 | 2018-06-29 | 湖北兴欣科技股份有限公司 | A kind of polyethylene hot-melt adhesive and its preparation method and application |
| CN106700974A (en) * | 2016-12-18 | 2017-05-24 | 钦州市科学技术开发中心 | Environmental-protection high-strength adhesive and preparation method thereof |
| CN107011838A (en) * | 2017-04-27 | 2017-08-04 | 安徽国登管业科技有限公司 | Steel plastic compount bonding material and preparation method thereof |
| CN107254024A (en) * | 2017-06-01 | 2017-10-17 | 安徽国登管业科技有限公司 | It is a kind of for adhering resin of steel-plastics composite pipe and preparation method thereof |
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| CN108192541A (en) * | 2017-12-26 | 2018-06-22 | 上海邦中高分子材料有限公司 | A kind of lining plastic composited pipe binding resin, preparation method and purposes |
| CN109679531A (en) * | 2018-12-27 | 2019-04-26 | 江苏鸿硕工程塑料科技股份有限公司 | A kind of continuous fiber prepreg tape PE adhesive and preparation method thereof |
| CN109837040A (en) * | 2019-03-01 | 2019-06-04 | 广东聚益新材有限公司 | Adhesive and its preparation method and application, glued board |
| CN111154427A (en) * | 2019-12-30 | 2020-05-15 | 河源市普立隆新材料科技有限公司 | Aluminum ceiling glue film structure and aluminum ceiling structure 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 |
| CN111471408A (en) * | 2020-04-09 | 2020-07-31 | 海油发展珠海管道工程有限公司 | Polyethylene composite belt and preparation, joint coating process method and application thereof |
| CN112976700A (en) * | 2021-02-08 | 2021-06-18 | 常熟市中电机械设备有限公司 | Polymer steel skeleton polymerization pipeline and preparation method thereof |
| CN115612424A (en) * | 2022-12-21 | 2023-01-17 | 广州鹿山新材料股份有限公司 | High-temperature-resistant adhesive and preparation method and application thereof |
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