CN103184692A - 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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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 the 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, also is one of requisite part of mass transport, also is 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 is also more and more simultaneously.Conveyer belt is mainly used in harbour now, mine, the transportation of industries such as machinery and food.Conveying has many types, generally distinguishes 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 conveyer belt etc.
Flame retardant conveyor belt is divided into PVC conveyer belt and PVG conveyer belt, and lower caldding layer is PVC lid glue on the PVC type, and lower caldding layer is acrylonitrile-butadiene rubber and PVC and usefulness on the PVG type.PVC type fire retarding conveying band belongs to light-duty conveyer belt, its main application is bread, cake, food-processing industry and accurate instrument such as aquatic products processing, electronic product, the goods of close mechanical etc. is carried, and also has printing, fields such as carpenter in addition, also has agricultural machinery, transport the agricultural product after the cleaning, fruit, tealeaves etc.
Why the PVC conveyer belt can be used in field so widely, mainly be because:
(l) the conveyer belt own wt is low weight, so friction ratio is lower, expense is low comparatively speaking.
(2) can freely select the conveyer belt tone.
(3) have a lot of good character: resistance to water, fungus resistance, oil resistivity, resistance to acids and bases.
(4) have good electric conductivity, can avoid some because the accident that accumulation causes.
(5) nontoxic, food hygiene is good.
Present fire retarding conveying band producer great majority also are to use the polyester-cotton blend union duck to do the belt carcass of conveyer belt, replacement duck progressively, polyvinyl canvas.Why consumption is greatly because its price is compared duck and dimensional cotton canvas is low to the polyester-cotton blend canvas, and TENSILE STRENGTH is bigger.The consumption of polyester-cotton blend canvas is increasing in China.The polyester-cotton blend conveyer belt has a lot of excellent characteristics, and for example: characteristics such as pliability and groove forming character are good, low price are applicable to that mainly the short-distance and medium-distance of little bulk, powder material are carried.
Life-span relatively weak point be the more common problem of fire retarding conveying band, also be the factor that the restriction fire retarding conveying band enlarge to use.Chief reason is exactly that canvas core and cover layer break away 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 peel strength of cover layer and canvas core is crossed the low coefficient that resistance to wears that can directly influence 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, as the dissaving polymer (Hyper branched polymers) of dendritic macromole homologue be a kind of have highly branched, the polymer of tridimensional network, it has the advantage that a lot of macromolecules do not have, for example viscosity is low, highly dissoluble, be difficult for crystallization, intermolecular difficult winding, a large amount of functional end-group and the characteristics of great chemical reactivity, and its special construction has been given its special performances.Dissaving polymer all shows huge using value at numerous areas such as coating, adhesive, auxiliary rheological agents and supramolecular chemistry, nanosecond science and technology, biomaterial, photoelectric material, medicine deliveries at present.
Summary of the invention
For the relatively shorter problem of the low fire retarding conveying band life-span that causes of peel strength that solves above fire retarding conveying band cover layer and canvas core, the invention provides a kind of dissaving polymer that in fire retarding conveying band, uses as the belt carcass interfacial agents, after fire retarding conveying band uses this dissaving polymer belt carcass interfacial agents, the life-span that can improve conveyer belt greatly.
The present invention is achieved by the following measures:
The application of a kind of dissaving polymer in fire retarding conveying band belt carcass interfacial agents, described dissaving polymer is through the silane coupler end-blocking, and general molecular formula is
Wherein, n repeateding unit number, m represent the silane coupler number of end-blocking, and g represents hyperbranched algebraically.
G is 1 to 4 natural number, the algebraically of expression dissaving polymer;
Described application is made into alcohol-water solution with ethanol and water according to the ratio of 95:5, regulates pH to 4.4-5.5, adding dissaving polymer when stirring, and making its concentration is 0.01 mol/L～0.02 mol/L, hydrolysis 5min obtains dissaving polymer solution.
Described application is immersed in the fire retarding conveying band belt carcass in the described dissaving polymer solution, and taking-up is dried, and bakes 30 minutes in 100 ℃ of baking ovens, makes the PVC conveyer belt with cover layer through calendering, cooling forming.
Described application, described fire retarding conveying band belt carcass is the polyester-cotton blend canvas, cover layer is PVC.
Described application, described silane coupler are gamma-aminopropyl-triethoxy-silane.
Described application, described dissaving polymer obtains by following steps:
(1) AB
2Synthesizing of type monomer
With diisopropanolamine (DIPA) and succinic acid reaction, the distillation desolventizing obtains AB
2The type monomer;
(2) super-branched polyesteramide is synthetic
To AB
2Add toluene in the type monomer as the band aqua, add the good trimethylolpropane core molecule of dissolving, add p-methyl benzenesulfonic acid as catalyst for reaction, at N
2In the atmosphere, magnetic agitation and heating reflux, and with the water that water knockout drum generates except dereaction, insulation reaction, the decompression distillation desolventizing obtains super-branched polyesteramide;
(3) silane coupler end-blocking
Synthetic good super-branched polyesteramide is dissolved in N, adds reaction unit in the dinethylformamide again, take out air and nitrogen protection in the system; add initator; gamma-aminopropyl-triethoxy-silane is added drop-wise in the reaction unit, and 40 ℃ were 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).
Trimethylolpropane and AB in the described application, step (2)
2When the mol ratio of type monomer is 1:9, obtain second generation dissaving polymer.
Trimethylolpropane and AB in the described application, step (2)
2When the mol ratio of type monomer is 1:21, obtain third generation dissaving polymer.
Trimethylolpropane and AB in the described application, step (2)
2When the mol ratio of type monomer is 1:45, obtain the 4th generation dissaving polymer.
Described application is characterized in that in the step (3) that catalyst for reaction is three to fluoridize the roc ethylether, and its quality is 0.5% of reactant gross mass.
Some special natures of utilizing dissaving polymer to follow traditional linear macromolecule to compare to have, its molecular structure with unique 3 D stereo shape makes its strand not have prehensile and no crystallinity.Its viscosity is low, and solubility property is good, when molecular weight increases or concentration when improving, still can keep lower viscosity, and terminally has a large amount of active groups and make it can be used for modification or introduce the group of needs.Its building-up process is relatively simple, and the separation that does not need to carry out multistep is purified, and 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 the polyester-cotton blend canvas is carried out modification, can make the polyester-cotton blend canvas have the unexistent performance of common cotton canvas, make that bonding strength improves greatly between itself and the cover layer, thereby prolong the service life of conveyer belt.
The specific embodiment
Below the preparation method of dissaving polymer of the present invention is described in more detail, its purpose is to illustrate design of the present invention and characteristics, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Example 1
The 6.660g diisopropanolamine (DIPA) that (1) will take by weighing moves into having in thermometer and the water knockout drum there-necked flask of assembling, the succinic anhydride that then 5.005g is dissolved in 20mLDMAc slowly is added drop-wise in the there-necked flask, also use magnetic agitation when dripping, decompression distillation desolventizing behind the reaction 3h obtains AB
2The type monomer;
(2) at synthetic AB
2Add 40mL toluene in the type monomer as the band aqua, add the 0.745g trimethylolpropane as core molecule (core molecule and AB
2The mol ratio of type monomer is 1:9), after dissolving fully by the time, add the Catalyzed by p-Toluenesulfonic Acid agent of monomer gross mass 0.5%, feed N
2, magnetic agitation and heating, temperature is controlled 170 ℃ of backflows, with the water that water knockout drum generates except dereaction, insulation reaction 7h, decompression distillation desolventizing after having reacted.Obtain light yellow viscous liquid, product is second generation super-branched polyesteramide;
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Synthetic good super-branched polyesteramide in the step (2) is dissolved in 40mLN, in the dinethylformamide, add reaction unit again, get 70.92g silane coupler gamma-aminopropyl-triethoxy-silane and place constant pressure funnel (mol ratio of silane coupler and super-branched polyesteramide is 12:1)., vacuumize repeatedly then, and logical nitrogen, remove the air in the reaction unit.The initator three that adds reactant gross mass 0.5% is fluoridized the roc ethylether, slowly drips silane coupler, is incubated 40 ℃ of reactions 24 hours, uses toluene and washed with methanol then, and 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 above-mentioned synthetic dissaving polymer when stirring, making its concentration is 0.01mol/L, and hydrolysis 5min gets the solution of dissaving polymer.
Performance test: the polyester-cotton blend canvas is dried in baking oven, will dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that is made into 5 minutes, dry under the room temperature, baked 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, 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, add dissaving polymer synthetic in above-described embodiment 1 when stirring, making its concentration is 0.02mol/L, hydrolysis 5min.
Performance test: the polyester-cotton blend canvas is dried in baking oven.To dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that (4) be made into 5 minutes, dry under the room temperature, bake 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
Example 3
The 9.990g diisopropanolamine (DIPA) that (1) will take by weighing moves into having in thermometer and the water knockout drum there-necked flask of assembling, the succinic anhydride that then 7.505g is dissolved in 30mLDMAc slowly is added drop-wise in the there-necked flask, also use magnetic agitation when dripping, decompression distillation desolventizing behind the reaction 3h obtains AB
2The type monomer.
(2) at above-mentioned synthetic AB
2Add 100mL toluene in the type monomer as the band aqua, add the 0.48g trimethylolpropane as core molecule (core molecule and AB
2The mol ratio of type monomer is 1:21), after dissolving fully by the time, add the p-methyl benzenesulfonic acid of monomer gross mass 0.5% as catalyst, feed N
2, magnetic agitation and heating, temperature is controlled 170 ℃ of backflows, with the water that water knockout drum generates except dereaction, insulation reaction 7h.Decompression distillation desolventizing after having reacted.Obtain light yellow viscous liquid, product is third generation super-branched polyesteramide.
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Synthetic good super-branched polyesteramide in (2) is dissolved in 40mLN, in the dinethylformamide, adds reaction unit again.Get 141.84g silane coupler gamma-aminopropyl-triethoxy-silane and place also funnel (mol ratio of silane coupler and super-branched polyesteramide is 24:1) of constant voltage ground, vacuumize repeatedly then, and logical nitrogen, remove the air in the reaction unit.The initator three that adds reactant gross mass 0.5% is fluoridized the roc ethylether, slowly drips silane coupler, is incubated 40 ℃ of reactions 24 hours, uses toluene and washed with methanol then, and 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 above-mentioned synthetic dissaving polymer when stirring, making its concentration is 0.01mol/L, hydrolysis 5min.
Performance test: the polyester-cotton blend canvas is dried in baking oven.To dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that (4) be made into 5 minutes, dry under the room temperature, bake 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, 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, add dissaving polymer synthetic in above-described embodiment 3 when stirring, making its concentration is 0.02mol/L, hydrolysis 5min.
Performance test: the polyester-cotton blend canvas is dried in baking oven.To dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that (4) be made into 5 minutes, dry under the room temperature, bake 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
Example 5
The 9.990g diisopropanolamine (DIPA) that (1) will take by weighing moves into having in thermometer and the water knockout drum there-necked flask of assembling, the succinic anhydride that then 7.505g is dissolved in 30mLDMAc slowly is added drop-wise in the there-necked flask, also use magnetic agitation when dripping, decompression distillation desolventizing behind the reaction 3h obtains AB
2The type monomer.
(2) at above-mentioned synthetic AB
2Add 100mL toluene in the type monomer as the band aqua, add the 0.225g trimethylolpropane as core molecule (core molecule and AB
2The mol ratio of type monomer is 1:45), after dissolving fully by the time, add the p-methyl benzenesulfonic acid of monomer gross mass 0.5% as catalyst, feed N
2, magnetic agitation and heating, temperature is controlled 170 ℃ of backflows, with the water that water knockout drum generates except dereaction, insulation reaction 7h.Decompression distillation desolventizing after having reacted.Obtain light yellow viscous liquid, product is third generation super-branched polyesteramide.
(3) dissaving polymer of synthesizing silane coupler end-blocking:
Synthetic good super-branched polyesteramide in (2) is dissolved in 40mLN, in the dinethylformamide, adds reaction unit again.Get 212.76g silane coupler gamma-aminopropyl-triethoxy-silane and place also funnel (mol ratio of silane coupler and super-branched polyesteramide is 48:1) of constant voltage ground, vacuumize repeatedly then, and logical nitrogen, remove the air in the reaction unit.The initator three that adds reactant gross mass 0.5% is fluoridized the roc ethylether, slowly drips silane coupler, is incubated 40 ℃ of reactions 24 hours, uses toluene and washed with methanol then, and 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 above-mentioned synthetic dissaving polymer when stirring, making its concentration is that 0.01mol/L(is originally 0.02mol/L), hydrolysis 5min.
Performance test: the polyester-cotton blend canvas is dried in baking oven.To dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that (4) be made into 5 minutes, dry under the room temperature, bake 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, 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, add dissaving polymer synthetic in above-described embodiment 5 when stirring, making its concentration is 0.02mol/L, hydrolysis 5min.
Performance test: the polyester-cotton blend canvas is dried in baking oven.To dry the polyester-cotton blend canvas handled then and immerse in the solution of the dissaving polymer that (4) be made into 5 minutes, dry under the room temperature, bake 30 minutes in 100 ℃ of baking ovens, cool off stand-by.The PVC muddle is covered on the polyester-cotton blend canvas of handling well with dissaving polymer, then through calendering, cooling.Then ready-made conveyer belt performance is tested.
Performance test:
1, according to standard HG/T 2410-2006 sampling,
2, sample specification:
(1) test specimen shape: 200mm * 25mm,
(2) layer of cloth: 2 layers,
(3) conveyer belt thickness: 3mm,
3, plunger bond strength:
Binder material to above-mentioned 6 examples has carried out performance test (GB/T 6759-2002), and data are as follows:
| The 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 |
Annotate: all sample peak-peaks must not surpass 20N/mm.
Fire retarding conveying band belt carcass interfacial agents commonly used at present has epoxy resin, neoprene adhesive, silane coupler etc.The 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 among the embodiment 3,4 respectively, and the bonding peel strength data of test is as follows:
| Concentration mol/L | The bonding peel strength, N/mm 〉= |
| 0.24 | 4.63 |
| 0.48 | 5.78 |
Compare with embodiment 3,4 bonding peel strength, use the fire retarding conveying band belt carcass interfacial agents of dissaving polymer, than the interfacial agents of simple use silane coupler, it is high a lot of that the bonding peel strength is wanted.
Above-described embodiment has only carried out the test experiments of aspect of performance to the PVC fire retarding conveying band, but because the belt carcass material of PVG fire retarding conveying band and PVC fire retarding conveying band is basic identical, therefore those skilled in the art are according to foregoing description, be to infer, dissaving polymer of the present invention is in the PVG fire retarding conveying band, also be to bring into play identical effect, just differing at this one has illustrated for example.
Claims (10)
1. the application of dissaving polymer in fire retarding conveying band belt carcass interfacial agents is characterized in that described dissaving polymer through the silane coupler end-blocking, and general molecular formula is
G is 1 to 4 natural number, the algebraically of expression dissaving polymer.
2. application according to claim 1, it is characterized in that ethanol and water are made into alcohol-water solution according to the ratio of 95:5, regulate pH to 4.4-5.5, when stirring, add dissaving polymer, making its concentration is 0.01 mol/L～0.02 mol/L, and hydrolysis 5min obtains dissaving polymer solution.
3. application according to claim 2 is characterized in that the fire retarding conveying band belt carcass is immersed in the described dissaving polymer solution, and taking-up is dried, and bakes 30 minutes in 100 ℃ of baking ovens, makes the PVC conveyer belt with cover layer through calendering, cooling forming.
4. application according to claim 2 is characterized in that described fire retarding conveying band belt carcass is the polyester-cotton blend canvas, and cover layer is PVC.
5. application according to claim 1 is characterized in that described silane coupler is gamma-aminopropyl-triethoxy-silane, and the mol ratio of itself and super-branched polyesteramide is (3*2
g): 1.
6. application according to claim 4 is characterized in that described dissaving polymer obtains by following steps:
(1) AB
2Synthesizing of type monomer
With diisopropanolamine (DIPA) and succinic acid reaction, the distillation desolventizing obtains AB
2The type monomer;
(2) super-branched polyesteramide is synthetic
To AB
2Add toluene in the type monomer as the band aqua, add the good trimethylolpropane core molecule of dissolving, add p-methyl benzenesulfonic acid as catalyst for reaction, at N
2In the atmosphere, magnetic agitation and heating reflux, and with the water that water knockout drum generates except dereaction, insulation reaction, the decompression distillation desolventizing obtains super-branched polyesteramide;
(3) silane coupler end-blocking
Synthetic good super-branched polyesteramide is dissolved in N, adds reaction unit in the dinethylformamide again, take out air and nitrogen protection in the system; add initator; gamma-aminopropyl-triethoxy-silane is added drop-wise in the reaction unit, and 40 ℃ were reacted 24 hours, and flushing is drying to obtain.
7. application according to claim 5 is characterized in that trimethylolpropane and AB in the step (2)
2When the mol ratio of type monomer is 1:9, obtain second generation dissaving polymer.
8. application according to claim 5 is characterized in that trimethylolpropane and AB in the step (2)
2When the mol ratio of type monomer is 1:21, obtain third generation dissaving polymer.
9. application according to claim 5 is characterized in that trimethylolpropane and AB in the step (2)
2When the mol ratio of type monomer is 1:45, obtain the 4th generation dissaving polymer.
10. application according to claim 5 is characterized in that in the step (3) that catalyst for reaction is three to fluoridize the roc ethylether, and its addition content is 0.5% of reactant gross mass.
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