CN103184692B - Application of hyperbranched polymer in belt core interface agent of flame-retardant conveying belt - Google Patents
Application of hyperbranched polymer in belt core interface agent of flame-retardant conveying belt Download PDFInfo
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- CN103184692B CN103184692B CN201310125661.2A CN201310125661A CN103184692B CN 103184692 B CN103184692 B CN 103184692B CN 201310125661 A CN201310125661 A CN 201310125661A CN 103184692 B CN103184692 B CN 103184692B
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Abstract
The invention relates to the technical field of flame-retardant conveying belts, and in particular relates to application of hyperbranched polymer in a belt core interface agent of a flame-retardant conveying belt, wherein the hyperbranched polymer is terminated by a silane coupling agent. Polyester cotton canvas is modified by the hyperbranched polymer and can obtain the performance unavailable to common canvas, the bonding strength with a covering layer is greatly improved, and the service life of a conveying belt is prolonged.
Description
technical field
The present invention relates to fire retarding conveying band technical field, the particularly application of dissaving polymer in fire retarding conveying band belt carcass interfacial agents.
background technology
Conveyer belt is the second largest industrial products after tire, is also one of requisite part of mass transport, is also one of indispensable part of national economy.Along with improving constantly of China's scientific and technological level and mechanical level, the consumption of conveyer belt is also increasing, and kind also gets more and more simultaneously.Present conveyer belt is mainly used in harbour, mine, the transport of the industries such as machinery and food.Conveying, with many types, is generally distinguished according to belt carcass, can be divided into fabric core conveyor belt, steel cable core conveying belt, haulage cable core conveyer belt (steel cable conveyor belt) and steel mesh conveying belt etc.
Flame retardant conveyor belt is divided into PVC conveyer belt and PVG conveyer belt, and in PVC type, lower caldding layer is PVC lid glue, and in PVG type, lower caldding layer is acrylonitrile-butadiene rubber and PVC and uses.PVC type fire retarding conveying band belongs to light-type conveyer belt, its main application is bread, cake, the food-processing industries such as aquatic products processing and accurate instrument, electronic product, the goods conveying of close mechanical etc., also has printing, the fields such as carpenter in addition, also has agricultural machinery, transport the agricultural product after cleaning, fruit, tealeaves etc.
PVC conveyer belt why can in field application so widely, mainly because:
L () conveyer belt own wt is relatively lighter, so friction ratio is lower, expense is low comparatively speaking.
(2) can unrestricted choice conveyer belt tone.
(3) there is much excellent character: resistance to water, fungus resistance, oil resistivity, resistance to acids and bases.
(4) there is excellent electric conductivity, can be avoided some because the accident of accumulation initiation.
(5) nontoxic, food hygiene is excellent.
Present fire retarding conveying band producer great majority or use polyester-cotton blend union duck do the belt carcass of conveyer belt, replacement duck progressively, polyvinyl canvas.Why consumption is greatly because its price compares duck and dimensional cotton canvas is low to polyester-cotton blend canvas, and TENSILE STRENGTH is larger.The consumption of polyester-cotton blend canvas is increasing in China.Polyester-cotton blend conveyer belt has a lot of excellent feature, such as: the features such as pliability and groove forming character is good, low price, is mainly applicable to the short-distance and medium-distance conveying of little bulk, powder material.
It is the more common problem of fire retarding conveying band that life-span is shorter, is also that restriction fire retarding conveying band expands the factor used.Chief reason is exactly that canvas core and cover layer depart from, and causes conveyer belt to be broken.Peel strength is one of important performance indexes of conveyer belt, and the size of peel strength directly determines serviceability and the life-span of conveyer belt.The too low meeting of peel strength of cover layer and canvas core directly affects the coefficient that resistance to wears of conveyer belt, has a strong impact on the service life of conveyer belt.
Highly branched polymer is one of hot issue of field of polymer technology research in recent decades, it is highly branched that dissaving polymer (Hyper branched polymers) as dendritic macromole homologue is that one has, the polymer of tridimensional network, it has the advantage that a lot of macromolecule does not have, such as viscosity is low, highly dissoluble, not easily crystallization, to be intermolecularly not easily wound around, the feature of a large amount of functional end-groups and great chemical reactivity, its special construction imparts its special performance.Current dissaving polymer all shows huge using value at the numerous areas such as coating, adhesive, auxiliary rheological agents and supramolecular chemistry, nanosecond science and technology, biomaterial, photoelectric material, drug carrier.
summary of the invention
In order to solve shorter problem of above fire retarding conveying band cover layer and the peel strength of the canvas core low fire retarding conveying band life-span caused, the invention provides a kind of in fire retarding conveying band as belt carcass interfacial agents use dissaving polymer, fire retarding conveying band can improve the life-span of conveyer belt after using this dissaving polymer belt carcass interfacial agents greatly.
The present invention is achieved by the following measures:
The application of dissaving polymer in fire retarding conveying band belt carcass interfacial agents, described dissaving polymer is through silane coupler end-blocking, and general molecular formula is
，
Wherein, n repeateding unit number, m represents the silane coupler number of end-blocking, and g represents hyperbranched algebraically.
G is the natural number of 1 to 4, represents the algebraically of dissaving polymer;
Described application, is made into alcohol-water solution by ethanol and water according to the ratio of 95:5, regulates pH to 4.4-5.5, adds dissaving polymer, make its concentration be 0.01 mol/L ~ 0.02 mol/L while stirring, and hydrolysis 5min obtains dissaving polymer solution.
Described application, be immersed in described dissaving polymer solution by fire retarding conveying band belt carcass, taking-up is dried, and bakes 30 minutes in 100 DEG C of baking ovens, with cover layer through rolling, cooling forming makes PVC conveyer belt.
Described application, described fire retarding conveying band belt carcass is polyester-cotton blend canvas, and cover layer is PVC.
Described application, described silane coupler is gamma-aminopropyl-triethoxy-silane.
Described application, described dissaving polymer is obtained by following steps:
(1) AB
2the synthesis of type monomer
Diisopropanolamine (DIPA) and succinic acid are reacted, distillation, except desolventizing, obtains AB
2type monomer;
(2) synthesis of super-branched polyesteramide
To AB
2add toluene in type monomer as water entrainer, add the trimethylolpropane core molecule dissolved, add the catalyst of p-methyl benzenesulfonic acid as reaction, at N
2in atmosphere, magnetic agitation also heats, backflow, the water generated except dereaction with water knockout drum, insulation reaction, and decompression distillation, except desolventizing, obtains super-branched polyesteramide;
(3) silane coupler end-blocking
Synthetic super-branched polyesteramide is dissolved in DMF and adds reaction unit again, pump the air in system and nitrogen protection; add initator; be added drop-wise to by gamma-aminopropyl-triethoxy-silane in reaction unit, 40 DEG C are reacted 24 hours, and flushing is drying to obtain.The mol ratio of silane coupler and super-branched polyesteramide is (3*2
g): 1(g is the algebraically of super-branched polyesteramide).
Described application, trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:9, obtain second generation dissaving polymer.
Described application, trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:21, obtain third generation dissaving polymer.
Described application, trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:45, obtain forth generation dissaving polymer.
Described application, it is characterized in that the catalyst of reaction in step (3) is borontrifluoride roc ethylether, its quality is 0.5% of reactant gross mass.
Utilize dissaving polymer to follow traditional linear macromolecule to compare some had special natures, its molecular structure with unique 3 D stereo shape makes its strand without prehensile and nodeless mesh.Its viscosity is low, and solubility property is good, when molecular weight increase or concentration improve time, still can keep lower viscosity, and end with a large amount of active groups make its can be used for modification or introduce need group.Its building-up process is relatively simple, and do not need the separating-purifying carrying out multistep, preparation is simple, and production cost is lower, is applicable to the production of heavy industrialization.
Beneficial effect of the present invention:
With dissaving polymer, modification is carried out to polyester-cotton blend canvas, polyester-cotton blend canvas can be made to have the unexistent performance of common cotton canvas, bonding strength between itself and cover layer is improved greatly, thus extend the service life of conveyer belt.
Detailed description of the invention
Below the preparation method of dissaving polymer of the present invention is described in more detail, its object is to design of the present invention and feature are described, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
example 1
(1) by the 6.660g diisopropanolamine (DIPA) taken move into assemble with in thermometer and water knockout drum there-necked flask, then succinic anhydride 5.005g being dissolved in 20mLDMAc is slowly added drop-wise in there-necked flask, also by magnetic agitation while dripping, after reaction 3h, decompression distillation is except desolventizing, obtains AB
2type monomer;
(2) at the AB of synthesis
2add 40mL toluene in type monomer as water entrainer, add 0.745g trimethylolpropane as core molecule (core molecule and AB
2the mol ratio of type monomer is 1:9), after by the time dissolving completely, add the Catalyzed by p-Toluenesulfonic Acid agent of monomer gross mass 0.5%, pass into N
2, magnetic agitation also heats, and temperature controls 170 DEG C of backflows, the water generated except dereaction with water knockout drum, insulation reaction 7h, and after having reacted, decompression distillation is except desolventizing.Obtain light yellow viscous liquid, product is second generation super-branched polyesteramide;
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Synthetic super-branched polyesteramide in step (2) is dissolved in 40mLN, in dinethylformamide, add reaction unit again, get 70.92g silane coupler gamma-aminopropyl-triethoxy-silane and be placed in constant pressure funnel (mol ratio of silane coupler and super-branched polyesteramide is 12:1)., then repeatedly vacuumize, and logical nitrogen, the air in removing reaction unit.Add the borontrifluoride roc ethylether of initator of reactant gross mass 0.5%, slowly drip silane coupler, be incubated 40 DEG C of reactions 24 hours, then use toluene and washed with methanol, vacuumize, both can obtain target product.
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, add the dissaving polymer of above-mentioned synthesis, make its concentration be 0.01mol/L while stirring, hydrolysis 5min obtains the solution of dissaving polymer.
Performance test: dried in an oven by polyester-cotton blend canvas, the polyester-cotton blend canvas then crossed by drying and processing to immerse in the solution of the dissaving polymer be made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
example 2
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, while stirring, add the dissaving polymer of synthesis in above-described embodiment 1, make its concentration be 0.02mol/L, hydrolysis 5min.
Performance test: polyester-cotton blend canvas is dried in an oven.Then the polyester-cotton blend canvas crossed by drying and processing to immerse in the solution of the dissaving polymer that (4) are made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
example 3
(1) by the 9.990g diisopropanolamine (DIPA) taken move into assemble with in thermometer and water knockout drum there-necked flask, then succinic anhydride 7.505g being dissolved in 30mLDMAc is slowly added drop-wise in there-necked flask, also by magnetic agitation while dripping, after reaction 3h, decompression distillation is except desolventizing, obtains AB
2type monomer.
(2) at the AB of above-mentioned synthesis
2add 100mL toluene in type monomer as water entrainer, add 0.48g trimethylolpropane as core molecule (core molecule and AB
2the mol ratio of type monomer is 1:21), after by the time dissolving completely, the p-methyl benzenesulfonic acid adding monomer gross mass 0.5%, as catalyst, passes into N
2, magnetic agitation also heats, and temperature controls 170 DEG C of backflows, the water generated except dereaction with water knockout drum, insulation reaction 7h.After having reacted, decompression distillation is except desolventizing.Obtain light yellow viscous liquid, product is third generation super-branched polyesteramide.
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Super-branched polyesteramide synthetic in (2) is dissolved in 40mLN, in dinethylformamide, then adds reaction unit.Get 141.84g silane coupler gamma-aminopropyl-triethoxy-silane and be placed in constant voltage ground also funnel (mol ratio of silane coupler and super-branched polyesteramide is 24:1), then repeatedly vacuumize, and logical nitrogen, the air in removing reaction unit.Add the borontrifluoride roc ethylether of initator of reactant gross mass 0.5%, slowly drip silane coupler, be incubated 40 DEG C of reactions 24 hours, then use toluene and washed with methanol, vacuumize, both can obtain target product.
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, while stirring, add the dissaving polymer of above-mentioned synthesis, make its concentration be 0.01mol/L, hydrolysis 5min.
Performance test: polyester-cotton blend canvas is dried in an oven.Then the polyester-cotton blend canvas crossed by drying and processing to immerse in the solution of the dissaving polymer that (4) are made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
example 4
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, while stirring, add the dissaving polymer of synthesis in above-described embodiment 3, make its concentration be 0.02mol/L, hydrolysis 5min.
Performance test: polyester-cotton blend canvas is dried in an oven.Then the polyester-cotton blend canvas crossed by drying and processing to immerse in the solution of the dissaving polymer that (4) are made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
example 5
(1) by the 9.990g diisopropanolamine (DIPA) taken move into assemble with in thermometer and water knockout drum there-necked flask, then succinic anhydride 7.505g being dissolved in 30mLDMAc is slowly added drop-wise in there-necked flask, also by magnetic agitation while dripping, after reaction 3h, decompression distillation is except desolventizing, obtains AB
2type monomer.
(2) at the AB of above-mentioned synthesis
2add 100mL toluene in type monomer as water entrainer, add 0.225g trimethylolpropane as core molecule (core molecule and AB
2the mol ratio of type monomer is 1:45), after by the time dissolving completely, the p-methyl benzenesulfonic acid adding monomer gross mass 0.5%, as catalyst, passes into N
2, magnetic agitation also heats, and temperature controls 170 DEG C of backflows, the water generated except dereaction with water knockout drum, insulation reaction 7h.After having reacted, decompression distillation is except desolventizing.Obtain light yellow viscous liquid, product is third generation super-branched polyesteramide.
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Super-branched polyesteramide synthetic in (2) is dissolved in 40mLN, in dinethylformamide, then adds reaction unit.Get 212.76g silane coupler gamma-aminopropyl-triethoxy-silane and be placed in constant voltage ground also funnel (mol ratio of silane coupler and super-branched polyesteramide is 48:1), then repeatedly vacuumize, and logical nitrogen, the air in removing reaction unit.Add the borontrifluoride roc ethylether of initator of reactant gross mass 0.5%, slowly drip silane coupler, be incubated 40 DEG C of reactions 24 hours, then use toluene and washed with methanol, vacuumize, both can obtain target product.
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, while stirring, add the dissaving polymer of above-mentioned synthesis, make its concentration be that 0.01mol/L(is originally 0.02mol/L), hydrolysis 5min.
Performance test: polyester-cotton blend canvas is dried in an oven.Then the polyester-cotton blend canvas crossed by drying and processing to immerse in the solution of the dissaving polymer that (4) are made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
example 6
Be made into alcohol-water solution with ethanol and water according to weight 95:5, add acetic acid, make pH reach 4.4-5.5, while stirring, add the dissaving polymer of synthesis in above-described embodiment 5, make its concentration be 0.02mol/L, hydrolysis 5min.
Performance test: polyester-cotton blend canvas is dried in an oven.Then the polyester-cotton blend canvas crossed by drying and processing to immerse in the solution of the dissaving polymer that (4) are made into 5 minutes, dries, bake 30 minutes, cool stand-by in 100 DEG C of baking ovens under room temperature.On the polyester-cotton blend canvas that PVC paste coating and dissaving polymer are handled well, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
performance test:
1, sample according to standard HG/T 2410-2006,
2, sample specification:
(1) Specimen Shape: 200mm × 25mm,
(2) layer of cloth: 2 layers,
(3) conveyer belt thickness: 3mm,
3, plunger bond strength:
Carried out performance test (GB/T 6759-2002) to the binder material of above-mentioned 6 examples, data are as follows:
| Bonding peel strength, N/mm >= | |
| Embodiment 1 | 10.72 |
| Embodiment 2 | 11.85 |
| Embodiment 3 | 12.96 |
| Embodiment 4 | 12.91 |
| Embodiment 5 | 11.82 |
| Embodiment 6 | 11.73 |
Note: all sample peak-peaks must not more than 20N/mm.
Fire retarding conveying band belt carcass interfacial agents conventional at present has epoxy resin, neoprene adhesive, silane coupler etc.Silane coupler gamma-aminopropyl-triethoxy-silane is made into the solution-treated conveyer belt belt carcass of 0.24mol/L, 0.48mol/L concentration.The concentration of silane coupler is identical with concentration in embodiment 3,4 respectively, and the bonding peel strength data of test is as follows:
| Concentration mol/L | Bonding peel strength, N/mm >= |
| 0.24 | 4.63 |
| 0.48 | 5.78 |
Contrast with the bonding peel strength of embodiment 3,4, use the fire retarding conveying band belt carcass interfacial agents of dissaving polymer, than the simple interfacial agents using silane coupler, bonding peel strength wants high a lot.
Above-described embodiment has only carried out the test experiments of aspect of performance to PVC fire retarding conveying band, but because PVG fire retarding conveying band is substantially identical with the band core material of PVC fire retarding conveying band, therefore those skilled in the art are according to foregoing description, to infer, dissaving polymer of the present invention is in PVG fire retarding conveying band, also be to play identical effect, just differing at this one illustrates.
Claims (5)
1. the application of dissaving polymer in fire retarding conveying band belt carcass interfacial agents, is characterized in that described dissaving polymer is obtained by following steps:
(1) AB
2the synthesis of type monomer
Diisopropanolamine (DIPA) and succinic acid are reacted, distillation, except desolventizing, obtains AB
2type monomer;
(2) synthesis of super-branched polyesteramide
To AB
2add toluene in type monomer as water entrainer, add the trimethylolpropane core molecule dissolved, add the catalyst of p-methyl benzenesulfonic acid as reaction, at N
2in atmosphere, magnetic agitation also heats, backflow, the water generated except dereaction with water knockout drum, insulation reaction, and decompression distillation, except desolventizing, obtains super-branched polyesteramide;
(3) silane coupler end-blocking
Synthetic super-branched polyesteramide is dissolved in DMF and adds reaction unit again, pump the air in system and nitrogen protection, add initator, be added drop-wise to by gamma-aminopropyl-triethoxy-silane in reaction unit, 40 DEG C are reacted 24 hours, and flushing is drying to obtain;
Trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:9, obtain second generation super-branched polyesteramide;
Trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:21, obtain third generation super-branched polyesteramide;
Trimethylolpropane and AB in step (2)
2when the mol ratio of type monomer is 1:45, obtain forth generation super-branched polyesteramide;
Described gamma-aminopropyl-triethoxy-silane and the mol ratio of super-branched polyesteramide are (3*2
g): 1, g is the natural number of 2 to 4, represents the algebraically of super-branched polyesteramide.
2. application according to claim 1, ethanol and water is it is characterized in that to be made into alcohol-water solution according to the ratio of weight 95:5, regulate pH to 4.4-5.5, dissaving polymer is added while stirring, make its concentration be 0.01 mol/L ~ 0.02 mol/L, hydrolysis 5min obtains dissaving polymer solution.
3. application according to claim 2, it is characterized in that fire retarding conveying band belt carcass to be immersed in described dissaving polymer solution, taking-up is dried, and bakes 30 minutes in 100 DEG C of baking ovens, with cover layer through rolling, cooling forming makes PVC conveyer belt.
4. application according to claim 2, it is characterized in that described fire retarding conveying band belt carcass is polyester-cotton blend canvas, cover layer is PVC.
5. application according to claim 1, it is characterized in that the initator of reaction in step (3) is boron trifluoride ethylether, its addition content is 0.5% of reactant gross mass.
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| CN103865262B (en) * | 2014-03-27 | 2016-03-23 | 济南大学 | The application of hyperbranched polymer in waterproof roll |
| CN104130586B (en) * | 2014-07-17 | 2016-11-23 | 济南大学 | Grafted by super branched polymer SBS application in waterproof roll |
| CN106893112A (en) * | 2017-03-31 | 2017-06-27 | 苏州铂邦胶业有限公司 | A kind of dendritic macromole coupling agent and preparation method thereof |
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| CN102060988B (en) * | 2010-11-08 | 2012-07-04 | 济南大学 | Hydroxy-terminated hyperbranched polyamine-ester polymer and application thereof in microfluidic chip |
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