CN106634815A - Special metal-plastic composite enhanced hot-melt adhesive and high-performance composite tube - Google Patents
Special metal-plastic composite enhanced hot-melt adhesive and high-performance composite tube Download PDFInfo
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- CN106634815A CN106634815A CN201611187845.1A CN201611187845A CN106634815A CN 106634815 A CN106634815 A CN 106634815A CN 201611187845 A CN201611187845 A CN 201611187845A CN 106634815 A CN106634815 A CN 106634815A
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- Prior art keywords
- pur
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- plastic
- enhancement mode
- metal
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
- F16L9/147—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups comprising only layers of metal and plastics with or without reinforcement
Abstract
The invention provides a special metal-plastic composite enhanced hot-melt adhesive and a high-performance composite tube. The special metal-plastic composite enhanced hot-melt adhesive is prepared from the following raw materials in parts by weight: 40-46 parts of polyethylene graft maleic anhydride hot-melt adhesive resin, 50-56 parts of deionized water, 0.5-0.8 part of catalyst, 0.2-0.3 part of graphene oxide and 3.3-3.9 parts of absolute alcohol. The special metal-plastic composite enhanced hot-melt adhesive has very high adhesive strength with metals and excellent compatibility with high-density polyethylene; and due to the introduction of the graphene oxide, various physical properties of the hot-melt adhesive are enhanced to different degrees.
Description
Technical field
The invention belongs to composite pipe field, more particularly, to a kind of metal-plastic be combined special enhancement mode PUR and
High-performance composite pipe.
Background technology
In recent years, because metal-plastic composite pipe has the advantage of metal material and plastics concurrently, so obtaining extensive at home
Using.Wherein, steel/polyethylene (PE) joint product is (such as steel lining PE pipes, steel strip reinforced PE helical bellowses and 2PE anti-corrosive steel tubes
Deng) large usage quantity；However, PE (non-polar polymer) there is no bonding force and steel between, both interfaces must be according to
It is glued by certain adhesive (such as PUR).
Current PUR is mainly based on ethylene-acrylic acid copolymer (EAA), PE grafting systems：The former places one's entire reliance upon
Import, but the adhesive is expensive and supplies unstable；The latter at home aluminium/plastic composite with HMA researchs aspect report compared with
It is many, but report in terms of steel/plastic composite is with HMA researchs less；And its market-oriented product generally existing bonding force is high,
The shortcomings of smell is big.The present invention, by making enhancement mode PUR GO-PE-g-MAH by oneself, prepares one based on PE grafting masterbatch
The compound hot melt adhesive special (GO-PE-g-MAH) of steel wire/polyethylene (PE) of bonding force height, good processability is planted, and applies steel
The compound hot melt adhesive special (GO-PE-g-MAH) of silk screen/high density polyethylene (HDPE) (HDPE) prepares a kind of very-high performance steel wire/highly dense
Degree polyethylene (HDPE) composite pipe.
The content of the invention
In view of this, it is contemplated that proposing that a kind of metal-plastic is combined special enhancement mode PUR and high-performance is compound
Tubing, to solve the adhesive bonding force not big technical problem of strong, smell.
To reach above-mentioned purpose, the technical scheme is that what is be achieved in that：
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：40～46 parts；
Deionized water：50～56 parts；
Catalyst：0.5～0.8 part；
Graphene oxide：0.2～0.3 part；
Absolute alcohol：3.3～3.9 parts.
Preferably, the metal-plastic is combined special enhancement mode PUR and is prepared by the raw material including following parts by weight
And obtain：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：42 parts；
Deionized water：50 parts；
Catalyst：0.6 part；
Graphene oxide：0.22 part；
Absolute alcohol：3.6 part.
Further, the catalyst is the concentrated sulfuric acid, DIC (DIC) or dicyclohexyl diimine
(DCC)。
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：Research of Grafting Malaic Anhydride Onto Polyethylene type hot melt gum resin is placed in reactor, adds deionized water, 86
At a temperature of～90 DEG C constant temperature process make within 3～3.5 hours after Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, spend from
Sub- water is rinsed, and stops rinsing after the liquid shows neutral into reactor, and the Research of Grafting Malaic Anhydride Onto Polyethylene type after hydrolysis is heated
Glue is dried 24～28 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：Catalyst and graphene oxide are weighed, addition after graphene oxide is completely dissolved in the middle of absolute alcohol
Catalyst, is placed in 80～85 DEG C of insulating boxs after 20～30min of stirring, static to be evaporated, and obtains pre-reaction thing B.
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5～10min by low speed mixer, Jing is double
Screw extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
In granulation process, the catalysis of the Jing catalyst at high temperature of the Research of Grafting Malaic Anhydride Onto Polyethylene type PUR after hydrolysis
Effect, with surface of graphene oxide polar group dehydration condensation is carried out, and forms stable polymer GO-PE-g-MAH, i.e.,
Obtain metal-plastic and be combined special enhancement mode PUR.
Further, the double screw extruder is that draw ratio is 90.
High-performance steel silk screen/high density polyethylene (HDPE) obtained in special enhancement mode PUR is combined using above-mentioned metal-plastic
Composite pipe.
Relative to prior art, metal-plastic of the present invention is combined special enhancement mode PUR and has the advantage that：
(1) metal-plastic of the present invention is combined special enhancement mode PUR, compared with conventional PUR, has
More polar groups, can form more chemical bonds between metal, thus the bonding strength pole of the PUR and metal
It is high.PUR matrix itself is polyvinyl resin, and it has fabulous compatibility with high density polyethylene (HDPE), simultaneously because oxidation
The introducing of Graphene so that each side physical property of the PUR has obtained different raisings, its 180 ° of peel strengths are reachable
134～142N/25mm, improves more than 30%, and the shear strength of PUR and steel wire is up to 18.3～19.6MPa, improves
More than 40%.Particularly in terms of high temperature resistant, Vicat softening point brings up to 128 DEG C, the Long-Time Service under the conditions of 95 DEG C, material
Performance is almost undamped；
(2) applied metal-plastics of the present invention are combined high-performance steel silk screen/height prepared by special enhancement mode PUR
Density polyethylene composite pipe, compared with conventional steel wire/high-density polyethylene compound pipe, 18～21N/ of peel strength
Mm, is 1.3 times of traditional steel wire/high-density polyethylene compound pipe.
Specific embodiment
In addition to being defined, technical term used has universal with those skilled in the art of the invention in following examples
The identical meanings of understanding.Test reagent used in following examples, if no special instructions, is routine biochemistry reagent；It is described
Experimental technique, if no special instructions, is conventional method.
Maleic anhydride grafted polyethylene PUR used in embodiment 1-5, graphene oxide, catalyst, absolute alcohol
It is with deionized water commercially available.
The present invention is described in detail with reference to embodiment.
Embodiment 1
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：40 parts；
Deionized water：50 parts；
Catalyst：0.5 part；
Graphene oxide：0.3 part；
Absolute alcohol：3.5 part；
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：40 parts of Research of Grafting Malaic Anhydride Onto Polyethylene types are heated into gum resin to be placed in reactor, adds 50 parts of deionizations
Water, constant temperature is processed and makes within 3 hours Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, question response at a temperature of 88 ± 2 DEG C
After end, using deionized water rinsing, after the liquid shows neutral into reactor stop rinse, by hydrolysis after it is polycthylene grafted
Maleic anhydride type PUR is processed 24 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：0.5 part of DCC and 0.3 part of graphene oxide is weighed, graphene oxide is completely dissolved in into 3.5 parts without watery wine
DCC is added after in precise and appropriate, is placed in 80 DEG C of insulating boxs after stirring 20min, it is static to be evaporated, obtain pre-reaction thing B；
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
Embodiment 2
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：42 parts；
Deionized water：50 parts；
Catalyst：0.6 part；
Graphene oxide：0.22 part；
Absolute alcohol：3.6 part；
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：42 parts of Research of Grafting Malaic Anhydride Onto Polyethylene types are heated into gum resin to be placed in reactor, adds 50 parts of deionizations
Water, constant temperature is processed and makes within 3 hours Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, question response at a temperature of 88 ± 2 DEG C
After end, using deionized water rinsing, after the liquid shows neutral into reactor stop rinse, by hydrolysis after it is polycthylene grafted
Maleic anhydride type PUR is processed 24 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：Weigh 0.6 part of DCC and 0.22 part of graphene oxide, by graphene oxide be completely dissolved in 3.6 parts it is anhydrous
DCC is added after in the middle of alcohol, is placed in 80 DEG C of insulating boxs after stirring 20min, it is static to be evaporated, obtain pre-reaction thing B；
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
Embodiment 3
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：45 parts；
Deionized water：56 parts；
DIC：0.8 part；
Graphene oxide：0.3 part；
Absolute alcohol：3.8 part；
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：45 parts of Research of Grafting Malaic Anhydride Onto Polyethylene types are heated into gum resin to be placed in reactor, adds 56 parts of deionizations
Water, constant temperature is processed and makes within 3 hours Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, question response at a temperature of 88 ± 2 DEG C
After end, using deionized water rinsing, after the liquid shows neutral into reactor stop rinse, by hydrolysis after it is polycthylene grafted
Maleic anhydride type PUR is processed 24 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：0.8 part of DIC and 0.3 part of graphene oxide is weighed, graphene oxide is completely dissolved in into 3.8 parts without watery wine
DIC is added after in precise and appropriate, is placed in 80 DEG C of insulating boxs after stirring 20min, it is static to be evaporated, obtain pre-reaction thing B.
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
Embodiment 4
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：46 parts；
Deionized water：56 parts；
Catalyst：0.8 part；
Graphene oxide：0.3 part；
Absolute alcohol：3.9 part；
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：46 parts of Research of Grafting Malaic Anhydride Onto Polyethylene types are heated into gum resin to be placed in reactor, adds 56 parts of deionizations
Water, constant temperature is processed and makes within 3 hours Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, question response at a temperature of 88 ± 2 DEG C
After end, using deionized water rinsing, after the liquid shows neutral into reactor stop rinse, by hydrolysis after it is polycthylene grafted
Maleic anhydride type PUR is processed 24 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：0.3 part of DCC and 0.3 part of graphene oxide is weighed, graphene oxide is completely dissolved in into 3.9 parts without watery wine
DCC is added after in precise and appropriate, is placed in 80 DEG C of insulating boxs after stirring 20min, it is static to be evaporated, obtain pre-reaction thing B.
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
Embodiment 5
A kind of metal-plastic is combined special enhancement mode PUR, is prepared by the raw material including following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：46 parts；
Deionized water：50 parts；
The concentrated sulfuric acid：0.5 part；
Graphene oxide：0.2 part；
Absolute alcohol：3.9 part；
Above-mentioned metal-plastic is combined the preparation method of special enhancement mode PUR, comprises the steps：
Step 1：46 parts of Research of Grafting Malaic Anhydride Onto Polyethylene types are heated into gum resin to be placed in reactor, adds 50 parts of deionizations
Water, constant temperature is processed and makes within 3 hours Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis, question response at a temperature of 88 ± 2 DEG C
After end, using deionized water rinsing, after the liquid shows neutral into reactor stop rinse, by hydrolysis after it is polycthylene grafted
Maleic anhydride type PUR is processed 24 hours as in vacuum drier, obtains pre-reaction thing A；
Step 2：0.5 part of concentrated sulfuric acid and 0.2 part of graphene oxide are weighed, graphene oxide is completely dissolved in into 3.9 parts of nothings
The concentrated sulfuric acid is added after in the middle of water-alcohol, is placed in 80 DEG C of insulating boxs after stirring 20min, it is static to be evaporated, obtain pre-reaction thing B.
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
The metal-plastic that above-described embodiment 1-5 is obtained is combined into special enhancement mode PUR and control sample (particular type
Number be commercially available deer mountain EP252) carry out performance test, the performance test results see the table below：
As can be seen from the above table, the metal-plastic that technical scheme is prepared is combined special enhancement mode heat
Melten gel is improved to some extent compared with PUR general on market in terms of peel strength, shear strength and softening performance.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (6)
1. a kind of metal-plastic is combined special enhancement mode PUR, it is characterised in that：The PUR is by including following parts by weight
Raw material be prepared：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：40～46 parts；
Deionized water：50～56 parts；
Catalyst：0.5～0.8 part；
Graphene oxide：0.2～0.3 part；
Absolute alcohol：3.3～3.9 parts.
2. metal-plastic according to claim 1 is combined special enhancement mode PUR, it is characterised in that：The PUR by
It is prepared including the raw material of following parts by weight：
Research of Grafting Malaic Anhydride Onto Polyethylene type heats gum resin：42 parts；
Deionized water：50 parts；
Catalyst：0.6 part；
Graphene oxide：0.22 part；
Absolute alcohol：3.6 part.
3. metal-plastic according to claim 1 and 2 is combined special enhancement mode PUR, it is characterised in that：The catalysis
Agent is the concentrated sulfuric acid, DIC or dicyclohexyl diimine.
4. arbitrary described metal-plastic is combined the preparation method of special enhancement mode PUR in claim 1-3, and its feature exists
In：Comprise the steps：
Step 1：Research of Grafting Malaic Anhydride Onto Polyethylene type hot melt gum resin is placed in reactor, adds deionized water, 86～90
Constant temperature is processed and made within 3～3.5 hours after Research of Grafting Malaic Anhydride Onto Polyethylene type PUR complete hydrolysis at a temperature of DEG C, deionized water
Rinse, stop rinsing after the liquid shows neutral into reactor, by the Research of Grafting Malaic Anhydride Onto Polyethylene type PUR after hydrolysis extremely
It is dried 24～28 hours in vacuum drier, obtains pre-reaction thing A；
Step 2：Catalyst and graphene oxide are weighed, catalysis is added after graphene oxide is completely dissolved in the middle of absolute alcohol
Agent, is placed in 80～85 DEG C of insulating boxs after 20～30min of stirring, static to be evaporated, and obtains pre-reaction thing B.
Step 3：Obtained pre-reaction thing A and pre-reaction thing B is sufficiently mixed into 5～10min, Jing twin-screws by low speed mixer
Extruder carries out granulation and obtains final product metal-plastic being combined special enhancement mode PUR.
5. the preparation method of special enhancement mode PUR, the twin-screw are combined according to the metal-plastic described in claim 4
It is 90 that extruder is draw ratio.
6. arbitrary described metal-plastic is combined high property obtained in special enhancement mode PUR in a kind of application claim 1-5
Can steel wire/high-density polyethylene compound pipe.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187845.1A CN106634815B (en) | 2016-12-20 | 2016-12-20 | The compound special enhanced hot melt adhesive of metal-plastic and high-performance composite pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187845.1A CN106634815B (en) | 2016-12-20 | 2016-12-20 | The compound special enhanced hot melt adhesive of metal-plastic and high-performance composite pipe |
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| CN106634815A true CN106634815A (en) | 2017-05-10 |
| CN106634815B CN106634815B (en) | 2018-08-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101301541B1 (en) * | 2011-12-29 | 2013-09-04 | 안영태 | A novel composite of graphene and non-polar polyolefins and a method for the preparation thereof |
| CN103361008A (en) * | 2012-04-02 | 2013-10-23 | 上海通悦包装材料有限公司 | Preparation method of hot melt adhesive composition |
| CN104371115A (en) * | 2014-11-26 | 2015-02-25 | 上海大学 | Polymer-grafted graphene oxide master batch and preparation method thereof |
| CN106117949A (en) * | 2016-07-12 | 2016-11-16 | 西华大学 | High-density polyethylene resin based nano composite material and preparation method thereof |
-
2016
- 2016-12-20 CN CN201611187845.1A patent/CN106634815B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101301541B1 (en) * | 2011-12-29 | 2013-09-04 | 안영태 | A novel composite of graphene and non-polar polyolefins and a method for the preparation thereof |
| CN103361008A (en) * | 2012-04-02 | 2013-10-23 | 上海通悦包装材料有限公司 | Preparation method of hot melt adhesive composition |
| CN104371115A (en) * | 2014-11-26 | 2015-02-25 | 上海大学 | Polymer-grafted graphene oxide master batch and preparation method thereof |
| CN106117949A (en) * | 2016-07-12 | 2016-11-16 | 西华大学 | High-density polyethylene resin based nano composite material and preparation method thereof |
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